WO2017091049A1 - Method for preparing wholly aromatic polyester resin and wholly aromatic polyester resin prepared thereby - Google Patents
Method for preparing wholly aromatic polyester resin and wholly aromatic polyester resin prepared thereby Download PDFInfo
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- WO2017091049A1 WO2017091049A1 PCT/KR2016/013783 KR2016013783W WO2017091049A1 WO 2017091049 A1 WO2017091049 A1 WO 2017091049A1 KR 2016013783 W KR2016013783 W KR 2016013783W WO 2017091049 A1 WO2017091049 A1 WO 2017091049A1
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- aromatic polyester
- wholly aromatic
- polyester resin
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- acid
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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
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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
- C08G63/133—Hydroxy compounds containing aromatic rings
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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
- C08G63/78—Preparation processes
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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
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
Definitions
- 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.
- 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.
- 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.
- 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.
- acetic acid gas acetic acid gas
- 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.
- 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.
- 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.
- 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 °C range.
- 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.
- 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
- the physical property of the wholly aromatic polyester resin finally manufactured can be made equal.
- 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.
- FIG. 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.
- 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.
- 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.
- the acetylation step may be performed for 1 to 3 hours in the temperature range of 140 ⁇ 160 °C.
- 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.
- 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.
- the acetylation step may be performed for 1 to 3 hours in the temperature range of 140 ⁇ 160 °C.
- 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.
- 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 °C.
- 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.
- 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.
- 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.
- the polycondensation reactor temperature is raised to a temperature range of 310 ⁇ 340 °C 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.
- 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 °C range of cooling water to the cooling jacket (4) automatically proceeds to stop It is characterized by.
- 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.
- cooling water is introduced into the cooling jacket 4, and the outlet pipe (10)
- 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 °C, 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.
- 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.
- 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.
- 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 °C.
- 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.
- 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.
- a grinder eg, a feather mill
- 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.
- the wholly aromatic polyester prepolymer may be cooled to a temperature of 20 ⁇ 70 °C. 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.
- 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.
- 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.
- 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 °C 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.
- 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.
- the temperature of the outlet pipe for discharging acetic acid and acetic anhydride generated in the polycondensation reaction tank is maintained at 140 °C, and the unreacted monomer and acetylated monomer are recovered in the polycondensation reaction tank to complete the polycondensation reaction.
- 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.
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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
본 발명은 전방향족 폴리에스테르 수지의 제조방법 및 이에 따라 제조된 전방향족 폴리에스테르 수지에 관한 것으로, 더욱 상세하게는 양산 스케일 중축합 반응에 의해 전방향족 폴리에스테르 수지를 제조하는 과정에서 배치별 전방향족 폴리에스테르 수지의 물성을 동등하게 제조할 수 있는 전방향족 폴리에스테르 수지의 제조방법 및 이에 따라 제조된 전방향족 폴리에스테르 수지에 관한 것이다.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.
전방향족 액정 폴리에스테르 수지는 전체가 방향족 사슬로만 이루어져 높은 내열성과 강도를 가지므로 고강도 및 고내열성을 요구하는 제품의 원재료로 중요하여 상업적으로 큰 응용성을 가진다.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.
전방향족 액정 폴리에스테르 수지는 흐름성 및 내열성이 우수하기 때문에 자동차 부품, 전기·전자부품, 소형·정밀 성형품의 재료로 널리 사용되고 있다.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.
이러한 전방향족 폴리에스테르의 중합은 최종고분자의 Tg, 녹는점 (결정성 경우), 열안정성, 용해성 등에 따라 어떤 중합반응을 적용할지 결정하게 된다. 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.
이러한 전방향족 폴리에스테르의 합성방법 중 가장 많이 사용되는 합성법은 용매를 사용하지 않고 용융법으로 중합하되 에스테르 교환반응을 이용한다. 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.
종래의 전방향족 폴리에스테르의 합성 방법은 하기와 같다.The synthesis method of the conventional wholly aromatic polyester is as follows.
한국등록특허 제1111645호에서는 방향족 히드록시 카르복실산, 방향족 디올 및 방향족 디카르복실산을 포함하되, 방향족 아미노 카르복실산은 포함하지 않는 원료 단량체를 중축합하여 전방향족 액정 폴리에스테르 프리폴리머를 합성하는 단계를 포함하고, 상기 방향족 디올은 2개의 페닐렌이 탄소가 아닌 원소로 결합된 방향족 화합물을 포함하지 않으며, 상기 원료 단량체 중 상기 방향족 디카르복실산의 함량은 상기 방향족 디올 1몰부에 대하여 1.02~1.08몰부인 전방향족 액정 폴리에스테르 수지의 제조방법을 게시하고 있다.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.
한국공개특허 제2010-0102923호에서는 (a) 초산금속 촉매를 사용하여 적어도 2종의 원료 단량체를 중축합함으로써 전방향족 액정 폴리에스테르 프리폴리머를 합성하는 단계; 및 (b) 상기 프리폴리머를 고상 중축합함으로써 전방향족 액정 폴리에스테르 수지를 합성하는 단계를 포함하는 전방향족 액정 폴리에스테르 수지의 제조방법을 게시하고 있다.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.
종래의 전방향족 폴리에스테르 수지를 제조하는 중축합 반응은 고온에서 진행되며 중축합 반응에 참여하지 못한 모노머 및 아세틸화된 모노머는 승화되어 초산 가스와 함께 유출되어 초기 투입된 모노머의 몰비와 중축합 반응에 참여하는 모노머의 몰비가 상이하게 됨으로써 배치별 전방향족 폴리에스테르 수지의 물성에 차이가 발생하는 문제점이 있다.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.
[선행기술문헌][Preceding technical literature]
[특허문헌][Patent Documents]
한국공개특허 제2010-0102923호 Korean Patent Publication No. 2010-0102923
한국등록특허 제0929383호Korean Registered Patent No. 0927383
일본공개 특개평10-158482Japanese Laid-Open Patent Publication No. 10-158482
상술한 종래기술의 문제점을 해결하기 위하여, 본 발명자들은 양산 스케일 중축합 반응에 의한 전방향족 폴리에스테르 수지의 제조 과정에서, 승화성을 갖는 중축합 반응에 참여하지 못한 모노머 및 아세틸화된 모노머가 고온에서 생성된 초산 가스와 함께 유출되는 것을 최소화하기 위한 기술에 대해 연구를 거듭하였고 그 결과 본 발명을 완성하기에 이르렀다.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.
따라서, 본 발명의 목적은 배치별 동등한 물성을 갖는 전방향족 폴리에스테르 수지의 제조방법 및 이에 따라 제조된 전방향족 폴리에스테르 수지를 제공하는데 있다.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.
상기와 같은 목적을 달성하기 위하여, 본 발명은 원료 단량체의 아세틸화 반응 및 에스테르화 반응을 수행하고 중축합시켜 프리폴리머를 제조하고, 상기 프리폴리머를 고상 중축합하여 전방향족 폴리에스테르 수지를 제조하는 방법에 있어서,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 ,
상기 원료 단량체를 중축합하여 프리폴리머를 제조하는 과정에서 유출관을 통해 초산 및 무수초산과 함께 배출되는 승화성 미반응 모노머 및 아세틸화된 모노머를 중축합 반응조로 회수하는 것을 특징으로 하는 전방향족 폴리에스테르 수지의 제조방법을 제공한다.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.
본 발명의 일 실시형태에 있어서, 상기 초산 및 무수초산과 함께 배출함과 동시에 미반응 모노머 및 아세틸화된 모노머를 중축합 반응조로 회수하기 위해 냉각수를 투입할 수 있는 냉각 재킷이 설치된 유출관을 사용할 수 있다.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.
본 발명의 일 실시형태에 있어서, 상기 유출관에는 유출관 상부 온도계가 설치되어 상부의 온도가 120~140 ℃ 범위로 유지될 수 있도록 냉각 재킷으로 유입되는 냉각수의 양을 조절하는 것이다.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.
본 발명의 일 실시형태에 있어서, 상기 유출관의 상부 온도가 120 ℃ 미만인 경우 냉각수의 투입이 중지될 수 있다.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.
또한, 본 발명은 상기 전방향족 폴리에스테르 수지의 제조방법을 포함하는 전방향족 폴리에스테르 수지 컴파운드의 제조방법 및 이에 따라 제조된 전방향족 폴리에스테르 수지 컴파운드를 제공한다.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.
또한, 본 발명은 방향족 폴리에스테르 수지를 제조하는 액상 중축합 반응에 사용하며 중축합 반응조로서, 생성된 초산 및 무수초산을 배출하기 위한 유출관; 상기 유출관의 상부에 구비된 유출관 상부 온도계; 및 상기 유출관에 냉각수를 공급하는 냉각 재킷을 포함하는 중축합 반응조를 제공한다.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.
본 발명은 양산 스케일 중축합 반응에 의한 전방향족 폴리에스테르 수지의 제조 공정에서, 중축합 반응에 참여하지 못한 모노머 및 아세틸화된 모노머가 고온에서 초산 가스와 함께 유출되는 것을 최소화하여 초기 투입된 원료 모노머의 몰비를 유지시켜 중축합 반응을 수행함으로써 최종 제조되는 전방향족 폴리에스테르 수지의 물성을 동등하게 할 수 있다.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.
또한, 본 발명에 따라 제조된 전방향족 폴리에스테르 수지는 목적한 물성이 배치별 동등하게 발현되어 이를 성형하여 제조되는 자동차 부품, 전기·전자부품, 소형·정밀 성형품 등의 신뢰성을 높일 수 있다.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.
도 1은 본 발명에 따른 전방향족 폴리에스테르 수지의 제조 공정에서 사용되는 냉각 재킷이 구비된 유출관을 포함하는 중축합 반응조의 구조를 개략적으로 나타낸 개략도이다.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.
본 발명의 이점 및 특징, 그리고 그것들을 달성하는 방법은 첨부되는 도면과 함께 상세하게 후술되는 실시예를 참조하면 명확해질 것이다.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.
그러나, 본 발명은 이하에서 개시되는 실시예로 한정되는 것이 아니라 서로 다른 다양한 형태로 구현될 것이다.However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms.
본 명세서에서 본 실시예는 본 발명의 개시가 완전하도록 하며, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에게 발명의 범주를 완전하게 알려주기 위해 제공되는 것이다.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.
그리고 본 발명은 청구항의 범주에 의해 정의될 뿐이다.And the present invention is only defined by the scope of the claims.
따라서, 몇몇 실시예에서, 잘 알려진 구성 요소, 잘 알려진 동작 및 잘 알려진 기술들은 본 발명이 모호하게 해석되는 것을 피하기 위하여 구체적으로 설명되지 않는다.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.
본 명세서에서, 단수형은 문구에서 특별히 언급하지 않는 한 복수형도 포함하며, '포함(또는, 구비)한다'로 언급된 구성 요소 및 동작은 하나 이상의 다른 구성요소 및 동작의 존재 또는 추가를 배제하지 않는다.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. .
다른 정의가 없다면, 본 명세서에서 사용되는 모든 용어(기술 및 과학적 용어를 포함)는 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에게 공통적으로 이해될 수 있는 의미로 사용될 수 있을 것이다.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.
또 일반적으로 사용되는 사전에 정의되어 있는 용어들은 정의되어 있지 않은 한 이상적으로 또는 과도하게 해석되지 않는다.In addition, the terms defined in the commonly used dictionary are not ideally or excessively interpreted unless they are defined.
이하, 본 발명에 따른 전방향족 폴리에스테르 수지의 제조방법을 상세하게 설명한다.Hereinafter, the manufacturing method of the wholly aromatic polyester resin which concerns on this invention is demonstrated in detail.
본 발명에 따른 전방향족 폴리에스테르 수지의 제조방법은 히드록시기를 갖는 방향족 단량체를 산 무수물과 반응시켜 아세틸화하는 단계(아세틸화 단계), 상기 아세틸화된 방향족 단량체를 방향족 디카르복실산과 에스테르화 반응 및 액상 중축합하여 전방향족 폴리에스테르 프리폴리머를 합성하는 단계(에스테르화 반응 및 액상 중축합 단계) 및 상기 전방향족 폴리에스테르 프리폴리머를 고상 중축합하여 전방향족 폴리에스테르 수지를 합성하는 단계(고상 중축합 단계)를 포함한다.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.
원료 단량체 중 히드록시기를 갖는 방향족 단량체의 아세틸화 반응에서는 아세틸화제로 무수초산 등을 사용하여 방향족 단량체의 히드록시기를 아세틸기로 충분히 치환시키고 부생성물로서 초산이 생성된다. 부생성물인 초산은 생성물로부터 가스 상태로 제거될 수 있다.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.
본 발명의 일 실시형태에 있어서, 상기 아세틸화 단계는 140~160 ℃의 온도 범위에서 1~3 시간 동안 진행될 수 있다. 상기 온도 및 시간이 각각 상기 범위 이내이면, 상기 방향족 단량체의 수산기가 아세틸기로 충분히 전환되어 이후 에스테르화 반응 및 액상 중축합이 저온에서 진행될 수 있고, 이에 따라 합성된 전방향족 폴리에스테르 프리폴리머가 열화되지 않아 상기 프로폴리머의 갈변 현상이 발생하지 않는다.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.
상기 원료 단량체로서 방향족 히드록시 카르복실산은 파라 히드록시 벤조산 및 2-히드록시-6-나프토에산 중 적어도 1종의 화합물을 포함할 수 있고, 상기 방향족 디올은 바이페놀 및 하이드로퀴논 중 적어도 1종의 화합물을 포함할 수 있고, 상기 방향족 디카르복실산은 이소프탈산, 나프탈렌 디카르복실산 및 테레프탈산으로 이루어진 군에서 선택되는 적어도 1종의 화합물을 포함할 수 있고, 전방향족 폴리에스테르 수지의 제조에 사용될 수 있는 공지의 원료 단량체를 더 포함할 수 있다.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.
본 발명의 일 실시형태에 있어서, 상기 아세틸화 단계는 140~160 ℃의 온도 범위에서 1~3 시간 동안 진행될 수 있다. 상기 온도 및 시간이 각각 상기 범위 이내이면, 상기 방향족 단량체의 히드록시기가 아세틸기로 충분히 전환되어 이후 에스테르화 반응 및 액상 중축합이 저온에서 진행될 수 있고, 이에 따라 합성된 전방향족 폴리에스테르 프리폴리머가 열화되지 않아 상기 프로폴리머의 갈변 현상이 발생하지 않는다.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.
상기 방향족 단량체의 아세틸화 단계는 용액 중축합법(solution condensation polymerization) 또는 괴상 중축합법(bulk condensation polymerization)에 의해 수행될 수 있다.Acetylation of the aromatic monomer may be performed by solution condensation polymerization or bulk condensation polymerization.
상기 아세틸화 단계에서는 반응 촉진을 위한 촉매로서 초산금속이 추가로 사용될 수 있다. 상기 초산금속 촉매는 초산마그네슘, 초산칼륨, 초산칼슘, 초산아연, 초산망간, 초산납, 초산안티몬 및 초산코발트로 이루어진 군으로부터 선택된 적어도 1종을 포함할 수 있다.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.
상기 에스테르화 반응 및 액상 중축합 단계는 310~340℃의 온도 범위에서 5~8시간 동안 진행될 수 있다. 상기 온도 및 시간이 각각 상기 범위 이내이면, 에스테르화 반응 및 액상 중축합 이후 배출 공정장애가 발생하지 않으며, 이후 고상 중축합 반응에 적합한 물성의 전방향족 폴리에스테르 프리폴리머를 얻을 수 있다.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.
본 발명에서는 상기 액상 중축합 단계에서 상기 아세틸화 반응 이후 부생성물로서 생성된 초산 및 미반응된 무수초산을 제거하는 공정을 수행하며, 상기 공정에서 중축합 반응에 참여하지 못한 모노머 및 아세틸화된 모노머가 고온에서 초산 가스와 함께 유출되지 않게 하여 최초 투입된 원료 단량체의 몰비를 유지시키면서 전방향족 폴리에스테를 제조함으로써 이의 물성이 배치별 동등하도록 하는 것을 특징으로 한다.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.
본 발명에서는 액상 중축합 반응시 도 1에 도시된 중축합 반응조(1)를 사용한다.In the present invention, the polycondensation reaction tank 1 shown in FIG. 1 is used in the liquid phase polycondensation reaction.
상기 중축합 반응조(1)는 생성된 초산 및 무수초산을 배출하기 위한 유출관(10); 상기 유출관의 상부에 구비된 유출관 상부 온도계(5); 및 상기 유출관에 냉각수를 공급하는 냉각 재킷(4)를 포함한다.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.
본 발명에서는 아세틸화 반응 및 중축합 반응 과정에서 생성된 초산과 미반응된 무수초산을 유출관(10)을 통해 제거하면서 중축합 반응기 온도를 310~340℃의 온도 범위로 승온시키는데 이때 반응 온도가 260℃ 이상이 되면 승화되는 모노머 및 아세틸화된 모노머의 양이 급격히 증가하게 된다.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.
따라서, 본 발명에서는 상기 미반응 모노머 및 아세틸화된 모노머를 중축합 반응조(1)로 회수하기 위해 냉각수를 투입할 수 있는 냉각 재킷(4)이 설치된 유출관(10)이 구비된 중축합 반응기(1)를 사용하며, 상기 유출관(10)에는 유출관 상부 온도계(5)가 설치되어 상부의 온도가 120~140℃ 범위를 벗어나게 되면 냉각 재킷(4)으로 냉각수의 투입 및 정지가 자동적으로 진행되는 것을 특징으로 한다.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.
즉, 본 발명에서는 미반응 모노머 및 아세틸화된 모노머가 초산 및 무수초산가 함께 유출관(10)을 통해 배출되지 않도록 유출관(10)의 상부 온도를 미반응 모노머 및 아세틸화된 모노머의 승화 온도 미만 및 초산 및 무수초산의 비점 이상인 120~140℃ 온도 범위로 조절한다.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.
보다 상세하게는, 본 발명에서는 유출관(10) 상부의 온도를 측정하여 초산 및 무수초산의 비점(boiling point)인 120~140℃ 보다 높아지면 냉각 재킷(4)으로 냉각수가 투입되고, 유출관(10) 상부의 온도가 120℃ 미만이 되면 냉각수 투입이 정지되도록 공정을 제어함으로써, 이를 통해 유출관(10)을 통해 낮은 비점을 갖는 초산과 무수초산만 부산물 회수드럼(3)으로 회수하고 고온의 승화성을 갖는 모노머 및 아세틸화된 모노머는 다시 중축합 반응조(1) 내부로 회수되어 반응에 참여하게 한다.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.
이에 따라, 본 발명에서의 전방향족 폴리에스테르의 중축합 반응은 회분식 반응이므로 각 배치별 투입된 모노머들의 비율에 맞는 중축합 반응이 진행되므로 생성된 전방향족 폴리에스테르 수지의 물성도 동등하게 된다.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.
상기 고상 중축합 단계가 수행되기 위해서는 상기 전방향족 폴리에스테르 프리폴리머에 적당한 열이 제공되어야 하며, 이러한 열 제공 방법으로는 가열판을 이용하는 방법, 열풍을 이용하는 방법, 고온의 유체를 이용하는 방법 등이 있다.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.
상기 전방향족 폴리에스테르 프리폴리머의 합성단계에는 반응 촉진을 위한 촉매로서 초산금속이 추가로 사용될 수 있다. 상기 초산금속 촉매는 초산마그네슘, 초산칼륨, 초산칼슘, 초산아연, 초산망간, 초산납, 초산안티몬, 초산코발트로 이루어진 군으로부터 선택된 적어도 1종을 포함할 수 있다. 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.
상기 전방향족 폴리에스테르 프리폴리머의 합성단계는 310~340℃의 온도 범위에서 5~8시간 동안 진행될 수 있다. 상기 온도 및 시간이 각각 상기 범위 이내이면, 중축합 반응후 배출 공정 장애가 발생하지 않으며, 고상 중축합 반응에 적합한 물성의 전방향족 폴리에스테르 프리폴리머를 얻을 수 있다.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.
본 발명의 일 실시형태에 있어서, 상기 전방향족 폴리에스테르 수지의 제조 방법은 상기 에스테르화 반응 및 액상 중축합 단계 이후 후술하는 고상 중합단계 이전에 상기 전방향족 폴리에스테르 프리폴리머를 분쇄하는 단계를 더 포함할 수 있다.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.
상기 분쇄된 전방향족 폴리에스테르 프리폴리머의 입자의 크기는 예를 들어, 0.5mm 내지 2.5mm일 수 있다.The particle size of the ground wholly aromatic polyester prepolymer may be, for example, 0.5mm to 2.5mm.
상기 전방향족 폴리에스테르 프리폴리머의 분쇄는 0.5mm~2.5mm의 메쉬 크기를 갖는 스크린이 내장된 분쇄기(예를 들어, Feather Mill)를 사용하여 수행될 수 있다.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.
본 발명의 일 실시형태에 있어서, 상기 전방향족 폴리에스테르 수지의 제조 방법은 상기 액상으로 에스테르화 반응을 진행하는 액상 중축합 단계와 상기 전방향족 폴리에스테르 프리폴리머 분쇄단계 사이에 상기 전방향족 폴리에스테르 프리폴리머를 냉각하는 단계를 추가로 포함할 수 있다. 상기 전방향족 폴리에스테르 프리폴리머의 냉각단계에서 상기 전방향족 폴리에스테르 프리폴리머는 20~70℃의 온도로 냉각될 수 있다. 이에 따라, 상기 전방향족 폴리에스테르 프리폴리머의 분쇄단계는 상기 전방향족 폴리에스테르 프리폴리머를 20~70℃의 온도로 유지한 상태에서 진행될 수 있다.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.
본 발명의 다른 구현예는 상기 전방향족 폴리에스테르 수지의 제조 방법에 의해 제조된 전방향족 폴리에스테르 수지 및 첨가제를 사용하는 전방향족 폴리에스테르 수지 컴파운드의 제조 방법을 제공한다.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.
상기 전방향족 폴리에스테르 수지 컴파운드의 제조 방법은, 전술한 전방향족 폴리에스테르 수지의 제조 방법에 따라 전방향족 폴리에스테르 수지를 합성하는 단계 및 상기 합성된 전방향족 폴리에스테르 수지와 첨가제를 용융혼련하는 단계를 포함할 수 있다. 이러한 용융혼련을 위하여 회분식 혼련기, 2축 압출기 또는 믹싱 롤 등이 사용될 수 있다. 또한, 원활한 용융혼련을 위하여 용융혼련시 활제를 사용할 수 있다.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.
상기 첨가제는 무기 충전제 및/또는 유기 충전제를 포함할 수 있다. 상기 무기 충전제는 유리섬유, 활석, 탄산칼슘, 운모, 점토 또는 이들 중 2 이상의 혼합물을 포함할 수 있으며, 상기 유기 충전제는 탄소섬유를 포함할 수 있다. 상기 무기 충전제와 유기 충전제는 상기 전방향족 폴리에스테르 수지 컴파운드의 사출성형시 사출성형품의 기계적 강도를 향상시키는 역할을 수행한다.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.
상기 용융혼련을 위하여 회분식 혼련기, 2축 압출기 또는 믹싱 롤 등이 사용될 수 있다. 또한, 원활한 용융혼련을 위하여 용융혼련시 활제를 사용할 수 있다.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.
상기와 같은 구성을 갖는 본 발명의 일 구현예에 따른 전방향족 폴리에스테르 수지 컴파운드는 이에 포함된 수지의 고내열성 (하중 변형 온도 250 ℃ 이상) 및 고유동성 특성으로 인해 전기전자 부품용에 적합한 엔지니어링 플라스틱을 제조하기에 적합하다.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.
이하, 실시예들을 들어 본 발명에 관하여 더욱 상세히 설명하지만, 본 발명이 이러한 실시예들에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
실시예Example
실시예 1 내지 5Examples 1-5
교반기, 환류장치 및 진공조절 장치를 갖춘 중축합 반응조를 파라-히드록시 벤조산 888kg, 바이페놀 399kg, 테레프탈산 267kg, 이소프탈산 89kg 및 무수초산 1,203kg을 투입하고, 질소분위기 하에서 아세트산 칼륨 0.13kg, 아세트산 마그네슘(4수화물) 0.495kg을 촉매로 투입 한 후 30분 동안 교반을 진행하였다. 열매를 순환시키며 반응기 온도를 1시간 동안 150℃로 승온시킨 후 2시간 동안 환류시키면서 아세틸화 반응을 진행하였다. 아세틸화 반응 및 중축합반응을 통해 생성된 초산을 제거하면서 반응기 온도를 320℃까지 6시간 동안 승온시켰다. 이때 중축합 반응조에서 생성된 초산을 회수하는 유출관은 상부의 온도가 140℃로 일정하게 유지되도록 하면서 중축합 반응을 진행하여 프리폴리머를 제조하였다. 회수된 부산물 중 미반응 모노머와 아세틸화된 모노머의 함량을 측정하였다. 중축합 반응이 완료된 프리폴리머를 반응기로부터 토출하면서 냉각시킨 후 분쇄기를 통해 평균 입경이 0.5~1.5mm 크기로 분쇄하였다. 균일한 크기로 분쇄된 프리폴리머를 회전식 고상반응기에 투입하고 250℃의 질소를 투입하면서 280℃까지 8시간에 걸쳐 승온시켰다. 이 온도에서 3시간 유지하면서 중축합반응을 완료시키고, 1시간 동안 100℃ 이하로 냉각시킨 후 전방향족 폴리에스터 수지를 회수하여 물성을 확인하였다. 동일한 중축합반응 조건에서 연속으로 5 배치(batch) (배치별 실시예 1 내지 실시예 5) 진행한 후 전방향족 폴리에스터 수지의 물성을 확인하여 하기 표 1에 나타내었다.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.
비교예 1 내지 5Comparative Examples 1 to 5
표 1에 기재된 바와 같이 액상중축합 반응시 유출관을 냉각시키지 않는 공정을 적용한 것을 제외하고는 실시예에 제시된 방법과 동일하게 연속으로 5 배치(batch) (배치별 비교실시예 1 내지 비교실시예 5) 진행한 후 전방향족 폴리에스테르 수지의 물성을 확인하여 하기 표 1에 나타내었다.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.
유출관상부 온도 (℃)Outlet Pipe Upper Temperature (℃) | 부산물 중 농도 (ppm)Concentration in by-products (ppm) | 전방향족 폴리에스테르 물성Fully aromatic polyester properties | ||||
미반응모노머Unreacted Monomer | 아세틸화 모노머Acetylated monomer | Tf (℃)Tf (℃) | Tm (℃)Tm (℃) | Mv(Poise)Mv (Poise) | ||
실시예 1Example 1 | 140140 | 33 | 1212 | 330330 | 351351 | 647647 |
실시예 2Example 2 | 140140 | 55 | 1818 | 330330 | 350350 | 639639 |
실시예 3Example 3 | 140140 | 44 | 1515 | 329329 | 350350 | 641641 |
실시예 4Example 4 | 140140 | 22 | 1515 | 331331 | 351351 | 652652 |
실시예 5Example 5 | 140140 | 33 | 1414 | 330330 | 350350 | 640640 |
비교예 1Comparative Example 1 | 178178 | 5858 | 129129 | 334334 | 356356 | 893893 |
비교예 2Comparative Example 2 | 181181 | 7373 | 184184 | 329329 | 350350 | 588588 |
비교예 3Comparative Example 3 | 180180 | 6565 | 179179 | 331331 | 352352 | 672672 |
비교예 4Comparative Example 4 | 179179 | 8585 | 166166 | 335335 | 355355 | 10071007 |
비교예 5Comparative Example 5 | 184184 | 107107 | 204204 | 338338 | 357357 | 13561356 |
상기 표 1을 참조하면, 중축합 반응조에서 생성된 초산 및 무수초산을 배출하는 유출관의 온도를 140 ℃로 유지하며 미반응 모노머와 아세틸화된 모노머를 중축합 반응조로 회수하여 중축합 반응을 완료하여 수행하는 경우, 중축합 반응시 유출관을 냉각시키지 않고 전방향족 폴리에스테르를 제조한 비교예 1 내지 5와 비교할 때 부산물의 농도가 현저하게 적었고 그에 따라 실시예 1 내지 5에서 제조된 전방향족 폴리에스테르의 물성은 유사하게 나타났다.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.
반면, 중축합 반응시 유출관을 냉각시키지 않고 전방향족 폴리에스테르를 제조한 비교예 1 내지 5에서 제조한 전방향족 폴리에스테르의 점도는 각 배치별 일정하지 않고 차이가 크게 나타났다.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.
이상의 설명은 본 발명의 기술 사상을 예시적으로 설명한 것에 불과한 것으로서, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 수정 및 변형이 가능할 것이다. 따라서, 본 발명에 개시된 실시예들은 본 발명의 기술 사상을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예에 의하여 본 발명의 기술 사상의 범위가 한정되는 것은 아니다. 본 발명의 보호 범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술 사상은 본 발명의 권리범위에 포함되는 것으로 해석되어야 할 것이다.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)
- 원료 단량체의 아세틸화 반응 및 에스테르화 반응을 수행하고 중축합시켜 프리폴리머를 제조하고, 상기 프리폴리머를 고상 중축합하여 전방향족 폴리에스테르 수지를 제조하는 방법에 있어서,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,상기 원료 단량체를 중축합하여 프리폴리머를 제조하는 과정에서 유출관을 통해 초산 및 무수초산과 함께 배출되는 승화성 미반응 모노머 및 아세틸화된 모노머를 중축합 반응조로 회수하는 것을 특징으로 하는 전방향족 폴리에스테르 수지의 제조방법.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.
- 청구항 1에 있어서,The method according to claim 1,상기 초산 및 무수초산과 함께 배출함과 동시에 미반응 모노머 및 아세틸화된 모노머를 중축합 반응조로 회수하기 위해 냉각수를 투입할 수 있는 냉각 재킷이 설치된 유출관을 사용하는 것을 특징으로 하는 전방향족 폴리에스테르 수지의 제조방법.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.
- 청구항 1에 있어서,The method according to claim 1,상기 유출관에는 유출관 상부 온도계가 설치되어 상부의 온도가 120~140 ℃에 도달하는 경우 냉각 재킷으로 냉각수가 투입되는 것을 특징으로 하는 전방향족 폴리에스테르 수지의 제조방법.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 ℃.
- 청구항 3에 있어서,The method according to claim 3,상기 유출관의 상부 온도가 120 ℃ 미만인 경우 냉각수의 투입이 중지되는 것을 특징으로 하는 전방향족 폴리에스테르 수지의 제조방법.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 ℃.
- 청구항 1에 있어서,The method according to claim 1,상기 원료 단량체는 방향족 히드록시 카르복실산, 방향족 디올, 방향족 디카르복실산 및 무수초산인 것을 특징으로 하는 전방향족 폴리에스테르 수지의 제조 방법.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.
- 청구항 5에 있어서,The method according to claim 5,상기 방향족 히드록시 카르복실산은 파라 히드록시 벤조산 및 2-히드록시-6-나프토에산 중 적어도 1종의 화합물을 포함하는 것을 특징으로 하는 전방향족 폴리에스테르 수지의 제조방법.And said aromatic hydroxy carboxylic acid comprises at least one compound of para hydroxy benzoic acid and 2-hydroxy-6-naphthoic acid.
- 청구항 5에 있어서,The method according to claim 5,상기 방향족 디올은 바이페놀 및 하이드로퀴논 중 적어도 1종의 화합물을 포함하는 것을 특징으로 하는 전방향족 폴리에스테르 수지의 제조방법.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.
- 청구항 5에 있어서,The method according to claim 5,상기 방향족 디카르복실산은 이소프탈산, 나프탈렌 디카르복실산 및 테레프탈산으로 이루어진 군으로부터 선택되는 적어도 1종의 화합물을 포함하는 것을 특징으로 하는 전방향족 폴리에스테르 수지의 제조방법.The aromatic dicarboxylic acid comprises at least one compound selected from the group consisting of isophthalic acid, naphthalene dicarboxylic acid and terephthalic acid.
- 청구항 1 내지 8 중 어느 한 항에 따른 전방향족 폴리에스테르 수지의 제조방법을 포함하는 전방향족 폴리에스테르 수지 컴파운드의 제조방법.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.
- 청구항 9항에 따라 제조된 전방향족 폴리에스테르 수지 컴파운드.A wholly aromatic polyester resin compound prepared according to claim 9.
- 청구항 1 내지 8 중 어느 한 항에 따라 제조되는 전방향족 폴리에스테르 수지.The wholly aromatic polyester resin prepared according to any one of claims 1 to 8.
- 방향족 폴리에스테르 수지를 제조하는 액상 중축합 반응에 사용하며 중축합 반응조로서,As a polycondensation reaction tank used in the liquid phase polycondensation reaction to prepare an aromatic polyester resin,생성된 초산 및 무수초산을 배출하기 위한 유출관;An outlet pipe for discharging the produced acetic acid and acetic anhydride;상기 유출관의 상부에 구비된 유출관 상부 온도계; 및An outlet tube upper thermometer provided at an upper portion of the outlet tube; And상기 유출관에 냉각수를 공급하는 냉각 재킷;A cooling jacket supplying cooling water to the outlet pipe;을 포함하는 중축합 반응조.Polycondensation reaction tank comprising a.
- 청구항 12에 있어서,The method according to claim 12,상기 유출관의 상부의 온도가 120~140 ℃에 도달하는 경우 냉각 재킷으로 냉각수가 투입되는 것을 특징으로 하는 중축합 반응조.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.
- 청구항 12에 있어서,The method according to claim 12,상기 유출관의 상부 온도가 120 ℃ 미만인 경우 냉각수의 투입이 중지되는 것을 특징으로 하는 중축합 반응조.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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