WO2017082710A1 - Method for producing wholly aromatic polyester resin with improved flowability, and wholly aromatic polyester produced thereby - Google Patents
Method for producing wholly aromatic polyester resin with improved flowability, and wholly aromatic polyester produced thereby Download PDFInfo
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- WO2017082710A1 WO2017082710A1 PCT/KR2016/013081 KR2016013081W WO2017082710A1 WO 2017082710 A1 WO2017082710 A1 WO 2017082710A1 KR 2016013081 W KR2016013081 W KR 2016013081W WO 2017082710 A1 WO2017082710 A1 WO 2017082710A1
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- aromatic polyester
- wholly aromatic
- polyester resin
- forming monomer
- producing
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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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
Definitions
- the present invention relates to a method for producing a wholly aromatic polyester resin with improved fluidity, and a wholly aromatic polyester prepared according to the present invention, and more particularly, to the high heat resistance and high flowability required for manufacturing an engineering plastic suitable for electrical and electronic parts. It relates to a method for producing a wholly aromatic polyester resin having, and a wholly aromatic polyester produced accordingly.
- the wholly aromatic polyester resin is made entirely of aromatic chains and has high heat resistance and strength, it is important as a raw material of high-strength fibers and has a large commercial applicability.
- the wholly aromatic polyester resin is excellent in flowability and heat resistance, it is used widely as a material of automobile parts, an electrical / electronic component, and a compact and precision molded article.
- the strength, heat resistance and molding processability of the liquid crystal polymer exhibit opposite characteristics.
- high crystallinity, glass transition temperature, high molecular weight, etc. are required, so it is difficult to obtain desired fluidity during molding.
- the molding temperature must also be a high temperature, the thermal stability based on the chemical structure is impaired. Therefore, it is necessary to develop a resin to secure molding fluidity while maintaining high strength, and to develop such a resin, it is necessary to control the composition of the polymer monomer.
- the wholly aromatic polyester using 1, 4- phenylenedicarboxylic acid, 1, 4- dihydroxy benzene, 4, 4'- dihydroxy biphenyl etc. as a copolymerization component has a high melting point of 350 degreeC or more, Too high for melt processing.
- various methods have been tried to lower the melting point to a temperature at which such a high melting point polyester can be processed by a general-purpose melt processing machine, but the mechanical strength at high temperatures (near the melting point) is realized while lowering the melting point to some extent. There is a problem that can not be maintained.
- Japanese Patent Application Laid-Open No. 81-10526 proposes a co-polyester in which 2-hydroxy-6-naphthoic acid, a diol component, and a dicarboxylic acid component are combined. There was a problem that the rate of liquefaction was high and the polymer was easily solidified at the outlet of the polymerization reactor.
- Japanese Patent Application Laid-Open No. 80-144024 proposes a copolyester obtained by combining 2-hydroxy-6-naphthoic acid, 4-hydroxybenzoic acid, a diol component, and a dicarboxylic acid component, but has problems in heat resistance and melt processability.
- the present inventors have conducted research to develop a technique for producing a wholly aromatic polyester resin having high heat resistance and high fluidity required for manufacturing an engineering plastic suitable for electrical and electronic parts. Again and again, the present invention has been completed.
- Another object of the present invention is to provide a wholly aromatic polyester resin having high heat resistance and high flowability suitable for producing engineering plastics suitable for electrical and electronic parts.
- 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 ,
- a refractive main chain forming monomer and a rigid linear structure forming monomer are used, and a content of the refractive main chain forming monomer is controlled according to the following Equation 1 to provide a method for producing a wholly aromatic polyester resin. .
- the refractive backbone forming monomer may include 6-hydroxy-2-naphthoic acid, and may further include isopropyl alcohol.
- the hard linear structure-forming monomer comprises biphenol, terephthalic acid and para hydroxy benzoic acid, and may further include paracetamol.
- the present invention also provides an wholly aromatic polyester resin prepared according to the above-mentioned method for producing an wholly aromatic polyester resin.
- the present invention also provides a method for producing an wholly aromatic polyester resin compound comprising the above-mentioned method for producing an wholly aromatic polyester resin.
- the present invention provides a wholly aromatic polyester resin compound prepared according to the method for producing a wholly aromatic polyester resin described above.
- the content of the refractory main chain forming monomer including para hydroxy benzoic acid among the raw material monomers used in the manufacturing process of the wholly aromatic polyester resin is used.
- a step of acetylating by reacting an aromatic monomer having a hydroxy group with an acid anhydride acetylation step
- esterifying the acetylated aromatic monomer with an aromatic dicarboxylic acid Synthesizing the wholly aromatic polyester prepolymer by polymerization reaction and liquid polycondensation (esterification reaction and liquid polycondensation step) and synthesizing the wholly aromatic polyester resin by solid phase polycondensation of the wholly aromatic polyester prepolymer (solid phase polycondensation step) ).
- the present invention uses a refractive main chain forming monomer and a hard linear structure forming monomer as a raw material monomer in the method for producing a wholly aromatic polyester resin through the above-described steps, the content of the refractive main chain forming monomer is It is characterized by being adjusted.
- the content of the refractive backbone forming monomer used as the raw material monomer in the present invention is less than 5.2 mol%, the wholly aromatic polyester resin produced is too rigid, so that the melting temperature (Tm) is high, but the flow initiation temperature (Tf) is high, thereby forming
- Tm melting temperature
- Tf flow initiation temperature
- workability is poor due to poor fluidity
- the content of the refraction backbone forming monomer exceeds 0.5 times mole% of the total content of the hard linear structure forming monomer, the flow initiation temperature (Tf) is lowered, but the high temperature heat resistance is lowered. Can be generated.
- the molar ratio of the refractive main chain forming monomer and hard linear structure forming monomer used as a raw material monomer in this invention is 1: 2.3-1: 9.
- the content of the refractive backbone forming monomer used as the raw material monomer in the present invention may be adjusted and added according to Equation 1, and such a control method may be easily performed by those skilled in the art.
- the term 'kinked backbone-forming monomer' has a bond structure at the ortho and meta positions of the benzene structure and has a naphthalene structure in a bent form rather than a symmetrical linear structure. It means a monomer. These monomers are believed to play a role in increasing the flexibility of the polymer structure and slowing down the crystallization rate to facilitate flowability and processability.
- the term 'rigid linear structure forming monomer' refers to a monomer having a straight structure in which the molecular structure is not flexible and having a binding structure only at the para position of the benzene structure. These hard monomers appear to contribute to the improvement of heat resistance by increasing the crystallinity.
- the refractive backbone forming monomer may include 6-hydroxy-2-naphthoic acid, and may further include isopropyl alcohol.
- the hard linear structure-forming monomer comprises biphenol, terephthalic acid and para hydroxy benzoic acid, and may further include paracetamol.
- 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.
- 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 condensation polymerization 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 condensation polymerization, and a wholly aromatic polyester prepolymer having physical properties suitable for the solid phase condensation reaction may be obtained.
- 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.
- By-products generated in the solid phase condensation polymerization step may be removed by purge or vacuum using an inert gas.
- 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 liquid crystal polyester prepolymer may be performed for 5 to 8 hours in the temperature range of 310 ⁇ 340 °C. When the temperature and time are within the above ranges, the discharge process failure does not occur after the polycondensation reaction, and a wholly aromatic liquid-crystalline polyester prepolymer suitable for the solid-phase polycondensation reaction can be obtained.
- 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 the liquid condensation polymerization 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 step of cooling the wholly aromatic polyester prepolymer between the esterification reaction and the liquid condensation polymerization step and the wholly aromatic polyester prepolymer grinding step It may further comprise.
- 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.
- the resin compression step may be further performed after synthesizing the wholly aromatic polyester resin.
- the resin extrusion step is a process for removing gas generated as unreacted monomers and by-products remaining in the wholly aromatic polyester resin.
- the resin extrusion step may be carried out at a temperature (ie, extrusion temperature) of more than the melting temperature (Tm) of the wholly aromatic polyester resin to less than Tm + 20 °C.
- Tm melting temperature
- the resin extrusion step is carried out within the temperature range, the unreacted monomer and / or acetic acid gas that the resin is sufficiently melted and remains effectively without deterioration (eg, carbonization) of the wholly aromatic polyester resin occurs. Can be removed.
- the extrusion temperature may be 340 ⁇ 360 °C.
- the resin extrusion step may be performed for a time of 3 to 8 seconds (ie, extrusion time).
- extrusion time When the extrusion time is within the range, it is possible to minimize the change in physical properties of the wholly aromatic polyester resin.
- 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 play a role of improving the mechanical strength of the injection molded article during the injection molding of the wholly aromatic liquid crystal 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 liquid-crystalline polyester resin compound according to an embodiment of the present invention having the configuration as described above is suitable for electrical and electronic parts due to the high heat resistance (load deformation temperature of 250 °C) and high fluidity characteristics of the resin contained therein It is suitable for producing plastics.
- Prepolymer was prepared by condensation polymerization at 330 ° C. for 6 hours.
- the prepared prepolymer was discharged from the reactor to be solidified by cooling, and then pulverized to an average particle size of 1 mm through a grinder.
- the uniformly pulverized prepolymer was introduced into a solid-phase reactor, a certain amount of nitrogen was purged, the temperature was raised to 330 ° C. over 5 hours, and then maintained at the same temperature for 3 hours for a transesterification reaction. After completion of the polycondensation reaction, the solid phase reactor was cooled for about 1 hour and the resulting polymer was recovered.
- Tm melting temperature
- DSC differential scanning calorimeter
- Tf flow initiation temperature
- a capillary flow meter with an internal diameter of 1 mm and a nozzle of 10 mm in length when the resin sample is extruded at a rate of 4 ° C./min and under a load condition of 100 kg / cm 2.
- the viscosity is measured at a temperature of 48,000 poise.
- a pellet of the wholly aromatic polyester resin was prepared in the same manner as in Example 1 except that the composition of the raw material monomers shown in Table 1 was used, and the load deformation temperature (DTUL) and the flow initiation temperature (Tf) of the prepared pellets were determined. It evaluated according to the following method and shown in Table 1.
- a pellet of the wholly aromatic polyester resin was prepared in the same manner as in Example 1 except that the composition of the raw material monomers shown in Table 1 was used, and the load deformation temperature (DTUL) and the flow initiation temperature (Tf) of the prepared pellets were determined. It evaluated according to the following method and shown in Table 1.
- HBA para hydroxy benzoic acid
- HNA 2-hydroxy-6-naphthoic acid
- BP biphenol
- TPA terephthalic acid
- IPA isophthalic acid
- APAP paracetamol
- the wholly aromatic polyester resin pellets of Examples 1 to 4 prepared by adjusting the amount of the raw material monomer used in the process of manufacturing the wholly aromatic polyester resin according to the present invention according to the formula 1 It can be seen that the deflection temperature under load is 270 ° C or higher, and the flow start temperature is 300 ° C or lower.
- the amount of the raw material monomer used in the preparation of the wholly aromatic polyester resin is out of the formula 1, the content of the refractive backbone forming monomer is higher than the molar ratio of the hard linear structure forming monomer used in Comparative Examples 1 and 2 It turns out that an aromatic polyester resin pellet has a load deformation temperature less than 250 degreeC.
- the wholly aromatic polyester resin pellets of Comparative Example 3 and Comparative Example 4 in which the content of the refractive backbone forming monomer was used at less than 5 mol% were easily operated with a load deformation temperature of 250 ° C. or higher but a flow start temperature of 300 ° C. or higher. You can see that you did not.
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- Polyesters Or Polycarbonates (AREA)
Abstract
Description
본 발명은 유동성이 향상된 전방향족 폴리에스테르 수지의 제조방법 및 이에 따라 제조된 전방향족 폴리에스테르에 관한 것으로, 더욱 상세하게는 전기전자 부품용에 적합한 엔지니어링 플라스틱을 제조하기 위해 필요한 고내열성 및 고유동성을 갖는 전방향족 폴리에스테르 수지의 제조방법 및 이에 따라 제조된 전방향족 폴리에스테르에 관한 것이다.The present invention relates to a method for producing a wholly aromatic polyester resin with improved fluidity, and a wholly aromatic polyester prepared according to the present invention, and more particularly, to the high heat resistance and high flowability required for manufacturing an engineering plastic suitable for electrical and electronic parts. It relates to a method for producing a wholly aromatic polyester resin having, and a wholly aromatic polyester produced accordingly.
전방향족 폴리에스테르 수지는 전체가 방향족 사슬로만 이루어져 높은 내열성과 강도를 가지므로 고강도 섬유의 원재료로 중요하여 상업적으로 큰 응용성을 가진다.Since the wholly aromatic polyester resin is made entirely of aromatic chains and has high heat resistance and strength, it is important as a raw material of high-strength fibers and has a large commercial applicability.
전방향족 폴리에스테르 수지는 흐름성 및 내열성이 우수하기 때문에 자동차 부품, 전기·전자부품, 소형·정밀 성형품의 재료로 널리 사용되고 있다.Since the wholly aromatic polyester resin is excellent in flowability and heat resistance, it is used widely as a material of automobile parts, an electrical / electronic component, and a compact and precision molded article.
일반적으로 액정 고분자의 강도 및 내열도와 성형가공성은 상반된 특성을 보인다. 고강도/고내열의 특성을 얻기 위해서는 높은 결정화도 및 유리전이 온도와 고분자량 등을 필요로 하기 때문에 성형시 원하는 유동성을 얻기 어렵다. 또한 강도 및 내열도를 높이기 위해 고융점화하면 성형 온도도 고온이 되어야 하기 때문에 화학구조를 토대로한 열안정성이 저해된다. 따라서 높은 강도를 유지하면서 성형유동성을 확보하기 위한 레진의 개발이 필요하며, 이러한 레진의 개발을 위해 고분자 단량체의 조성을 조절할 필요가 있다.In general, the strength, heat resistance and molding processability of the liquid crystal polymer exhibit opposite characteristics. In order to obtain high strength / high heat resistance properties, high crystallinity, glass transition temperature, high molecular weight, etc. are required, so it is difficult to obtain desired fluidity during molding. In addition, if the high melting point in order to increase the strength and heat resistance, the molding temperature must also be a high temperature, the thermal stability based on the chemical structure is impaired. Therefore, it is necessary to develop a resin to secure molding fluidity while maintaining high strength, and to develop such a resin, it is necessary to control the composition of the polymer monomer.
전방향족 폴리에스테르로서 현재 시판되고 있는 것은 4-하이드록시벤조산이 주성분이다. 그러나, 4-하이드록시벤조산의 단독중합체는 융점이 분해점보다도 높아져 버리기 때문에, 다양한 성분을 공중합함으로써 저융점화해야 한다.As a wholly aromatic polyester, what is currently marketed is 4-hydroxybenzoic acid as a main component. However, since the melting point of the homopolymer of 4-hydroxybenzoic acid becomes higher than the decomposition point, it is necessary to lower the melting point by copolymerizing various components.
공중합 성분으로서 1,4-페닐렌디카복실산, 1,4-디하이드록시벤젠, 4,4'-디하이드록시비페닐 등을 사용한 전방향족 폴리에스테르는 융점이 350℃ 이상으로 높아서 범용의 장치에 의해 용융 가공을 실시하기에는 지나치게 높다. 또한 이러한 융점이 높은 폴리에스테르를 범용의 용융 가공 기기로 가공할 수 있는 온도까지 융점을 내리기 위해서 다양한 방법이 시도되고 있지만, 저융점화가 어느 정도 실현되는 한편으로 고온(융점하 근방)에서의 기계적 강도를 유지할 수 없다는 문제가 있다.The wholly aromatic polyester using 1, 4- phenylenedicarboxylic acid, 1, 4- dihydroxy benzene, 4, 4'- dihydroxy biphenyl etc. as a copolymerization component has a high melting point of 350 degreeC or more, Too high for melt processing. In addition, various methods have been tried to lower the melting point to a temperature at which such a high melting point polyester can be processed by a general-purpose melt processing machine, but the mechanical strength at high temperatures (near the melting point) is realized while lowering the melting point to some extent. There is a problem that can not be maintained.
이러한 문제를 해결하기 위해서 일본특허공개 제81-10526호에서는 2-하이드록시-6-나프토산, 디올 성분, 디카복실산 성분을 조합시킨 공중합 폴리에스테르가 제안되었지만, 이 폴리에스테르는 냉각시의 고화(固化)속도가 빠르고, 중합 반응기의 배출구에서 중합체가 고화되기 쉽다는 문제가 있었다. 또한 일본특허공개 제80-144024호에서는 2-하이드록시-6-나프토산, 4-하이드록시벤조산, 디올 성분, 디카복실산 성분을 조합시킨 공중합 폴리에스테르가 제안되었지만 내열성, 용융 가공성에 문제가 있었다.In order to solve such a problem, Japanese Patent Application Laid-Open No. 81-10526 proposes a co-polyester in which 2-hydroxy-6-naphthoic acid, a diol component, and a dicarboxylic acid component are combined. There was a problem that the rate of liquefaction was high and the polymer was easily solidified at the outlet of the polymerization reactor. In addition, Japanese Patent Application Laid-Open No. 80-144024 proposes a copolyester obtained by combining 2-hydroxy-6-naphthoic acid, 4-hydroxybenzoic acid, a diol component, and a dicarboxylic acid component, but has problems in heat resistance and melt processability.
[선행기술문헌][Preceding technical literature]
[특허문헌][Patent Documents]
한국등록특허 제0773646호Korean Patent Registration No. 0773646
한국공개특허 제2010-0102923호 Korean Patent Publication No. 2010-0102923
한국등록특허 제0929383호Korean Registered Patent No. 0927383
일본공개 특개평10-158482 Japanese Laid-Open Patent Publication No. 10-158482
상술한 종래기술의 문제점을 해결하기 위하여, 본 발명자들은 전기·전자부품용에 적합한 엔지니어링 플라스틱을 제조함에 있어 필요한 고내열성 및 고유동성을 갖는 전방향족 폴리에스테르 수지를 제조하기 위한 기술을 개발하고자 연구를 거듭하였고 그 결과 본 발명을 완성하기에 이르렀다.In order to solve the above-mentioned problems of the prior art, the present inventors have conducted research to develop a technique for producing a wholly aromatic polyester resin having high heat resistance and high fluidity required for manufacturing an engineering plastic suitable for electrical and electronic parts. Again and again, the present invention has been completed.
따라서, 본 발명의 목적은 높은 강도 및 고내열성을 유지하면서 성형 유동성을 확보할 수 있는 전방향족 폴리에스테르 수지의 제조방법을 제공하는데 있다.Accordingly, it is an object of the present invention to provide a method for producing an wholly aromatic polyester resin capable of securing molding fluidity while maintaining high strength and high heat resistance.
본 발명의 다른 목적은 전기·전자부품용에 적합한 엔지니어링 플라스틱을 제조하기에 적합한 고내열성 및 고유동성을 갖는 전방향족 폴리에스테르 수지를 제공하는데 있다.Another object of the present invention is to provide a wholly aromatic polyester resin having high heat resistance and high flowability suitable for producing engineering plastics suitable for electrical and electronic parts.
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 단량체로는 굴절 주쇄 형성 단량체 및 경질 선형 구조 형성 단량체를 사용하며, 상기 굴절 주쇄 형성 단량체의 사용 함량은 하기 식 1에 따라 조절되는 것을 특징으로 하는 전방향족 폴리에스테르 수지의 제조방법을 제공한다.As the raw material monomer, a refractive main chain forming monomer and a rigid linear structure forming monomer are used, and a content of the refractive main chain forming monomer is controlled according to the following Equation 1 to provide a method for producing a wholly aromatic polyester resin. .
[식 1][Equation 1]
5.2 몰% < 굴절 주쇄 형성 단량체 함량 (몰%) < 0.5 × 경질 선형 구조 형성 단량체 함량 (몰%).5.2 mole% <refractive backbone forming monomer content (mole%) <0.5 x hard linear structure forming monomer content (mole%).
본 발명의 일 실시형태에 있어서, 상기 굴절 주쇄 형성 단량체는 6-히드록시-2-나프토에산을 포함하고, 이소프로필알코올을 더 포함할 수 있다.In one embodiment of the present invention, the refractive backbone forming monomer may include 6-hydroxy-2-naphthoic acid, and may further include isopropyl alcohol.
본 발명의 일 실시형태에 있어서, 상기 경질 선형 구조 형성 단량체는 바이페놀, 테레프탈산 및 파라 히드록시 벤조산을 포함하고, 파라세타몰을 더 포함할 수 있다.In one embodiment of the present invention, the hard linear structure-forming monomer comprises biphenol, terephthalic acid and para hydroxy benzoic acid, and may further include paracetamol.
또한, 본 발명은 상술한 전방향족 폴리에스테르 수지의 제조방법에 따라 제조된 전방향족 폴리에스테르 수지를 제공한다.The present invention also provides an wholly aromatic polyester resin prepared according to the above-mentioned method for producing an wholly aromatic polyester resin.
또한, 본 발명은 상술한 전방향족 폴리에스테르 수지의 제조방법을 포함하는 전방향족 폴리에스테르 수지 컴파운드의 제조방법을 제공한다. The present invention also provides a method for producing an wholly aromatic polyester resin compound comprising the above-mentioned method for producing an wholly aromatic polyester resin.
아울러, 본 발명은 상술한 전방향족 폴리에스테르 수지의 제조방법에 따라 제조된 전방향족 폴리에스테르 수지 컴파운드를 제공한다.In addition, the present invention provides a wholly aromatic polyester resin compound prepared according to the method for producing a wholly aromatic polyester resin described above.
본 발명에 따른 전방향족 폴리에스테르 수지의 제조방법은 전방향족 폴리에스테르 수지의 제조과정에서 사용하는 원료 단량체 중 파라 히드록시 벤조산을 포함하는 굴절 주쇄 형성 단량체의 사용함량을 경질 선형 구조 형성 단량체의 사용함량과의 특정 몰비로 조절함으로써 고온 내열성도 우수할뿐만 아니라 성형 유동성도 우수한 전방향족 폴리에스테르 수지를 제조할 수 있다.In the method for producing an wholly aromatic polyester resin according to the present invention, the content of the refractory main chain forming monomer including para hydroxy benzoic acid among the raw material monomers used in the manufacturing process of the wholly aromatic polyester resin is used. By controlling to a specific molar ratio of and it is possible to produce a wholly aromatic polyester resin not only excellent in high temperature heat resistance but also excellent in molding fluidity.
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 유동성이 향상된 전방향족 폴리에스테르 수지의 제조방법을 상세하게 설명한다.Hereinafter, the manufacturing method of the wholly aromatic polyester resin improved the fluidity | liquidity which concerns on this invention is demonstrated in detail.
본 발명에 따른 유동성이 향상된 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.In the method for producing a wholly aromatic polyester resin having improved fluidity according to the present invention, a step of acetylating by reacting an aromatic monomer having a hydroxy group with an acid anhydride (acetylation step), esterifying the acetylated aromatic monomer with an aromatic dicarboxylic acid Synthesizing the wholly aromatic polyester prepolymer by polymerization reaction and liquid polycondensation (esterification reaction and liquid polycondensation step) and synthesizing the wholly aromatic polyester resin by solid phase polycondensation of the wholly aromatic polyester prepolymer (solid phase polycondensation step) ).
본 발명은 상술한 단계를 거쳐 전방향족 폴리에스테르 수지를 제조하는 방법에서 원료 단량체로는 굴절 주쇄 형성 단량체 및 경질 선형 구조 형성 단량체를 사용하며, 상기 굴절 주쇄 형성 단량체의 사용 함량은 하기 식 1에 따라 조절되는 것을 특징으로 한다.The present invention uses a refractive main chain forming monomer and a hard linear structure forming monomer as a raw material monomer in the method for producing a wholly aromatic polyester resin through the above-described steps, the content of the refractive main chain forming monomer is It is characterized by being adjusted.
[식 1][Equation 1]
5.2 몰% < 굴절 주쇄 형성 단량체 함량 (몰%) < 0.5 × 경질 선형 구조 형성 단량체 함량 (몰%).5.2 mole% <refractive backbone forming monomer content (mole%) <0.5 x hard linear structure forming monomer content (mole%).
전방향족 폴리에스테르 수지를 제조하는 과정에서 상기 굴절 주쇄 형성 단량체의 사용 함량을 상기 식 1에 따라 조절함으로써 고내열성을 유지하면서도 성형 유동성 갖는 전방향족 폴리에스테르 수지를 제조할 수 있다.In the process of preparing the wholly aromatic polyester resin, by adjusting the content of the refractive backbone-forming monomer according to Equation 1, it is possible to prepare a wholly aromatic polyester resin having a molding fluidity while maintaining high heat resistance.
본 발명에서 원료 단량체로서 사용되는 굴절 주쇄 형성 단량체 함량이 5.2 몰% 미만인 경우 제조되는 전방향족 폴리에스테르 수지가 너무 경질(rigid)이여서 용융온도(Tm)가 높아지지만 유동 개시 온도(Tf)가 높아져 성형 유동성이 좋지 않아 가공성이 저하되는 문제점이 있고, 굴절 주쇄 형성 단량체 함량이 경질 선형 구조 형성 단량체 총 함량의 0.5 배 몰%를 초과하는 경우 유동 개시 온도(Tf)는 낮아지나 고온 내열성이 저하되는 문제점이 발생될 수 있다. When the content of the refractive backbone forming monomer used as the raw material monomer in the present invention is less than 5.2 mol%, the wholly aromatic polyester resin produced is too rigid, so that the melting temperature (Tm) is high, but the flow initiation temperature (Tf) is high, thereby forming There is a problem in that workability is poor due to poor fluidity, and when the content of the refraction backbone forming monomer exceeds 0.5 times mole% of the total content of the hard linear structure forming monomer, the flow initiation temperature (Tf) is lowered, but the high temperature heat resistance is lowered. Can be generated.
본 발명에서 원료 단량체로서 사용되는 굴절 주쇄 형성 단량체와 경질 선형 구조 형성 단량체의 몰비는 1:2.3~1:9인 것이 바람직하다.It is preferable that the molar ratio of the refractive main chain forming monomer and hard linear structure forming monomer used as a raw material monomer in this invention is 1: 2.3-1: 9.
본 발명에서 원료 단량체로서 사용되는 굴절 주쇄 형성 단량체 함량은 상기 식 1에 따라 조절하여 투입될 수 있고, 이러한 조절 방법은 당업자에 의해 용이하게 수행될 수 있다. The content of the refractive backbone forming monomer used as the raw material monomer in the present invention may be adjusted and added according to Equation 1, and such a control method may be easily performed by those skilled in the art.
본 발명에서 용어 ‘굴절 주쇄(kinked backbone) 형성 단량체'는 분자 구조가 대칭의 일자형 구조가 아닌 꺾인 형태로 벤젠구조의 오르토(ortho), 메타(meta) 위치에 결합구조를 갖거나 나프탈렌 구조를 갖는 단량체를 의미한다. 이러한 단량체는 고분자 구조의 유연성을 높이고 결정화 속도를 늦춰 유동성이나 가공성을 용이하게 해 주는 역할을 하는 것으로 추정된다.In the present invention, the term 'kinked backbone-forming monomer' has a bond structure at the ortho and meta positions of the benzene structure and has a naphthalene structure in a bent form rather than a symmetrical linear structure. It means a monomer. These monomers are believed to play a role in increasing the flexibility of the polymer structure and slowing down the crystallization rate to facilitate flowability and processability.
또한, 본 발명에서 용어 ‘경질 선형 구조(rigid linear structure) 형성 단량체'는 분자 구조가 유연하지 않는 일자형 구조를 갖는 것으로 벤젠구조의 파라(para) 위치에만 결합구조를 갖는 단량체를 의미한다. 이러한 경질의 단량체는 결정화도를 높여 내열성 향상에 기여하는 것으로 보인다.In addition, in the present invention, the term 'rigid linear structure forming monomer' refers to a monomer having a straight structure in which the molecular structure is not flexible and having a binding structure only at the para position of the benzene structure. These hard monomers appear to contribute to the improvement of heat resistance by increasing the crystallinity.
본 발명의 일 실시형태에 있어서, 상기 굴절 주쇄 형성 단량체는 6-히드록시-2-나프토에산을 포함하고, 이소프로필알코올을 더 포함할 수 있다.In one embodiment of the present invention, the refractive backbone forming monomer may include 6-hydroxy-2-naphthoic acid, and may further include isopropyl alcohol.
본 발명의 일 실시형태에 있어서, 상기 경질 선형 구조 형성 단량체는 바이페놀, 테레프탈산 및 파라 히드록시 벤조산을 포함하고, 파라세타몰을 더 포함할 수 있다.In one embodiment of the present invention, the hard linear structure-forming monomer comprises biphenol, terephthalic acid and para hydroxy benzoic acid, and may further include paracetamol.
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 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 축중합 단계는 310~340℃의 온도 범위에서 5~8시간 동안 진행될 수 있다. 상기 온도 및 시간이 각각 상기 범위 이내이면, 에스테르화 반응 및 액상 축중합 이후 배출 공정장애가 발생하지 않으며, 이후 고상 축중합 반응에 적합한 물성의 전방향족 폴리에스테르 프리폴리머를 얻을 수 있다.The esterification reaction and the liquid phase condensation polymerization 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 condensation polymerization, and a wholly aromatic polyester prepolymer having physical properties suitable for the solid phase condensation reaction may be obtained.
상기 고상 축중합 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. 상기 고상 축중합 단계에서 발생하는 부산물은 불활성 기체를 이용한 퍼지나 진공에 의하여 제거될 수 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. By-products generated in the solid phase condensation polymerization step may be removed by purge or vacuum using an inert gas.
상기 전방향족 액정 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 liquid crystal 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 액정 폴리에스테르 프리폴리머의 합성단계는 310~340℃의 온도 범위에서 5~8시간 동안 진행될 수 있다. 상기 온도 및 시간이 각각 상기 범위이내이면, 중축합 반응후 배출 공정장애가 발생하지 않으며, 고상 중축합반응에 적합한 물성의 전방향족 액정 폴리에스테르 프리폴리머를 얻을 수 있다.Synthesis of the wholly aromatic liquid crystal polyester prepolymer may be performed for 5 to 8 hours in the temperature range of 310 ~ 340 ℃. When the temperature and time are within the above ranges, the discharge process failure does not occur after the polycondensation reaction, and a wholly aromatic liquid-crystalline polyester prepolymer suitable for the solid-phase polycondensation reaction can be obtained.
본 발명의 일 실시형태에 있어서, 상기 전방향족 폴리에스테르 수지의 제조 방법은 상기 에스테르화 반응 및 액상 축중합 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 the liquid condensation polymerization 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 에스테르화 반응 및 액상 축중합 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 step of cooling the wholly aromatic polyester prepolymer between the esterification reaction and the liquid condensation polymerization step and the wholly aromatic polyester prepolymer grinding step It may further comprise. 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 일 실시형태에 있어서, 전방향족 폴리에스테르 수지를 합성한 후 수지 압축 단계를 더 수행할 수 있다.In one embodiment of the present invention, the resin compression step may be further performed after synthesizing the wholly aromatic polyester resin.
상기 수지 압출단계는 상기 전방향족 폴리에스테르 수지에 잔류하는 미반응 단량체 및 부산물로 발생하는 가스를 제거하기 위한 공정이다.The resin extrusion step is a process for removing gas generated as unreacted monomers and by-products remaining in the wholly aromatic polyester resin.
상기 수지 압출단계는 상기 전방향족 폴리에스테르 수지의 용융 온도(Tm) 이상 내지 Tm+20℃ 이하의 온도(즉, 압출온도)에서 실시될 수 있다. 상기 수지 압출단계가 상기 온도 범위 이내에서 수행되면, 상기 전방향족 폴리에스테르 수지의 열화(예를 들어, 탄화)가 일어나지 않으면서도 상기 수지가 충분히 용융되어 잔류하는 미반응 단량체 및/또는 초산 가스가 효과적으로 제거될 수 있다. 예를 들어, 상기 압출온도는 340~360℃일 수 있다.The resin extrusion step may be carried out at a temperature (ie, extrusion temperature) of more than the melting temperature (Tm) of the wholly aromatic polyester resin to less than Tm + 20 ℃. When the resin extrusion step is carried out within the temperature range, the unreacted monomer and / or acetic acid gas that the resin is sufficiently melted and remains effectively without deterioration (eg, carbonization) of the wholly aromatic polyester resin occurs. Can be removed. For example, the extrusion temperature may be 340 ~ 360 ℃.
상기 수지 압출단계는 3~8초의 시간(즉, 압출시간) 동안 진행될 수 있다. 상기 압출시간이 상기 범위이내이면, 상기 전방향족 폴리에스테르 수지의 물성 변화를 최소화할 수 있다.The resin extrusion step may be performed for a time of 3 to 8 seconds (ie, extrusion time). When the extrusion time is within the range, it is possible to minimize the change in physical properties of the wholly aromatic polyester resin.
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 액정 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 play a role of improving the mechanical strength of the injection molded article during the injection molding of the wholly aromatic liquid crystal 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 액정 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 liquid-crystalline polyester resin compound according to an embodiment of the present invention having the configuration as described above is suitable for electrical and electronic parts due to the high heat resistance (load deformation temperature of 250 ℃) and high fluidity characteristics of the resin contained therein It is suitable for producing plastics.
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
실시예Example 1 One
교반기, 환류장치 및 온도 조절 장치가 구비된 중축합 반응기에 하기 표 1에 기재된 중량에 따라 2-히드록시-6-나프토에산, 이소프탈산, 파라-히드록시 벤조산, 바이페놀, 테레프탈산 및 파라세타몰을 투입하고, 질소 분위기 하에서 무수초산을 투입하여 상온에서 30분간 교반하고 30분에 걸쳐 150℃까지 승온시킨다. 이후 초산칼륨과 초산마그네슘을 사용한 원료 단량체 총사용량 100 중량부 기준으로 각각 300ppm, 500ppm을 더 첨가한 후 3시간 가량 환류시켜 아세틸화 반응을 진행하였다. 이후 온도를 330℃까지 승온시켜 에스테르화 반응을 진행시키며 부산물로 생성된 초산을 응축기를 통해 제거하였다. 330℃에서 6시간 동안 유지시켜 축중합하여 프리폴리머를 제조하였다. 상기 제조된 프리폴리머를 반응기로부터 토출하여 냉각 고화시킨 후 분쇄기를 통해 평균 입경 1mm 크기로 분쇄하였다. 균일하게 분쇄된 프리폴리머를 고상반응기에 투입하고 일정량의 질소를 퍼지하며 5시간에 걸쳐 330℃까지 승온시킨 후 3시간 동안 같은 온도를 유지시켜 트랜스 에스테르화 반응을 시켰다. 축중합 반응을 완료한 후 고상 반응기를 1시간 가량 냉각시킨 후 생성된 중합체를 회수하였다.In a polycondensation reactor equipped with a stirrer, a reflux device and a temperature control device, 2-hydroxy-6-naphthoic acid, isophthalic acid, para-hydroxy benzoic acid, biphenol, terephthalic acid and paracetamol according to the weight shown in Table 1 below. The solution was added, acetic anhydride was added under a nitrogen atmosphere, stirred at room temperature for 30 minutes, and heated to 150 ° C. over 30 minutes. Thereafter, 300 ppm and 500 ppm were further added based on 100 parts by weight of the total amount of the raw material monomers using potassium acetate and magnesium acetate, and the mixture was refluxed for about 3 hours to proceed with the acetylation reaction. Then, the temperature was raised to 330 ° C. to proceed with the esterification reaction, and acetic acid produced as a byproduct was removed through a condenser. Prepolymer was prepared by condensation polymerization at 330 ° C. for 6 hours. The prepared prepolymer was discharged from the reactor to be solidified by cooling, and then pulverized to an average particle size of 1 mm through a grinder. The uniformly pulverized prepolymer was introduced into a solid-phase reactor, a certain amount of nitrogen was purged, the temperature was raised to 330 ° C. over 5 hours, and then maintained at the same temperature for 3 hours for a transesterification reaction. After completion of the polycondensation reaction, the solid phase reactor was cooled for about 1 hour and the resulting polymer was recovered.
상기 회수한 수지를 유리섬유(직경 10㎛, 길이 120~150㎛)가 30% 함유되도록 혼합 후 이축 압출기를 사용하여 용융 혼련하여 제조된 펠렛의 하중 변형 온도(DTUL) 및 유동 개시 온도(Tf)를 하기 방법에 따라 평가하여 표 1에 나타내었다.Load strain temperature (DTUL) and flow initiation temperature (Tf) of pellets prepared by melt kneading using a twin screw extruder after mixing the recovered resin to contain 30% of glass fibers (diameter 10 ㎛, length 120 ~ 150 ㎛) To evaluate according to the following method is shown in Table 1.
하중 변형 온도(DTUL) 측정 방법: 우선 사출기(FANUC Co. Ltd, S-2000i 50B)를 사용하여 상기 제조한 각 전방향족 액정 폴리에스테르 수지 컴파운드의 시편을 제작하였고, 상기 각 시편을 상온으로 냉각한 후 5시간 동안 방치한 다음 각 시편의 하중 변형 온도를 ASTM D648에 따라 측정한다.Method for measuring the deflection temperature (DTUL): First, specimens of each of the prepared aromatic aromatic liquid-crystalline polyester resin compounds were prepared using an injection machine (FANUC Co. Ltd, S-2000i 50B), and the specimens were cooled to room temperature. After standing for 5 hours, the load deflection temperature of each specimen is measured according to ASTM D648.
Tm(용융온도)은 시차 주사 열량계 (TA Instruments社, DSC 2910)를 사용하여 수지 시료를 40℃에서부터 20℃/분의 승온조건으로 가열하였을 때 흡열피크로 나타나는 온도로 측정한다.Tm (melting temperature) is measured by using a differential scanning calorimeter (DSC, DSC 2910) at the temperature indicated by the endothermic peak when the resin sample is heated from 40 ° C to 20 ° C / min.
Tf(유동 개시 온도)는 수지 시료를 4 ℃/분의 속도로 온도를 증가시키며 100 kg/cm 2 의 하중 조건으로 압출시키는 경우, 내부 직경 1 mm 및 길이 10 mm 의 노즐을 갖는 모세관 유량계로 용융 점도가 48,000 포이즈가 되는 온도로 측정한다.Tf (flow initiation temperature) is melted with a capillary flow meter with an internal diameter of 1 mm and a nozzle of 10 mm in length when the resin sample is extruded at a rate of 4 ° C./min and under a load condition of 100 kg / cm 2. The viscosity is measured at a temperature of 48,000 poise.
실시예Example 2 내지 4 2 to 4
하기 표 1에 기재된 원료 단량체의 조성을 사용한 것을 제외하고 실시예 1과 동일하게 수행하여 전방향족 폴리에스테르 수지의 펠렛을 제조하였고, 제조된 펠렛의 하중 변형 온도(DTUL) 및 유동 개시 온도(Tf)를 하기 방법에 따라 평가하여 표 1에 나타내었다.A pellet of the wholly aromatic polyester resin was prepared in the same manner as in Example 1 except that the composition of the raw material monomers shown in Table 1 was used, and the load deformation temperature (DTUL) and the flow initiation temperature (Tf) of the prepared pellets were determined. It evaluated according to the following method and shown in Table 1.
비교예Comparative example 1 내지 4 1 to 4
하기 표 1에 기재된 원료 단량체의 조성을 사용한 것을 제외하고 실시예 1과 동일하게 수행하여 전방향족 폴리에스테르 수지의 펠렛을 제조하였고, 제조된 펠렛의 하중 변형 온도(DTUL) 및 유동 개시 온도(Tf)를 하기 방법에 따라 평가하여 표 1에 나타내었다.A pellet of the wholly aromatic polyester resin was prepared in the same manner as in Example 1 except that the composition of the raw material monomers shown in Table 1 was used, and the load deformation temperature (DTUL) and the flow initiation temperature (Tf) of the prepared pellets were determined. It evaluated according to the following method and shown in Table 1.
HBA: 파라 히드록시 벤조산, HNA: 2-히드록시-6-나프토에산, BP: 바이페놀, TPA: 테레프탈산, IPA: 이소프탈산, APAP: 파라세타몰HBA: para hydroxy benzoic acid, HNA: 2-hydroxy-6-naphthoic acid, BP: biphenol, TPA: terephthalic acid, IPA: isophthalic acid, APAP: paracetamol
표 1을 참조하면, 본 발명에 따라 전방향족 폴리에스테르 수지를 제조하는 과정에서 사용하는 원료 단량체의 양을 상기 식 1에 따라 조절하여 투입하여 제조한 실시예 1 내지 4의 전방향족 폴리에스테르 수지 펠렛은 하중 변형 온도(Deflection Temperature under load)가 270℃ 이상이고, 유동 개시 온도가 300℃ 이하인 것을 알 수 있다.Referring to Table 1, the wholly aromatic polyester resin pellets of Examples 1 to 4 prepared by adjusting the amount of the raw material monomer used in the process of manufacturing the wholly aromatic polyester resin according to the present invention according to the formula 1 It can be seen that the deflection temperature under load is 270 ° C or higher, and the flow start temperature is 300 ° C or lower.
반면, 전방향족 폴리에스테르 수지를 제조하는 과정에서 사용하는 원료 단량체의 양이 식 1에 벗어나 굴절 주쇄 형성 단량체의 함량이 경질 선형 구조 형성 단량체의 몰비보다 높게 사용된 비교예 1 및 2에서 제조한 전방향족 폴리에스테르 수지 펠렛은 하중 변형 온도가 250℃ 미만인 것을 알 수 있다. 또한, 굴절 주쇄 형성 단량체의 함량이 5 몰% 미만으로 사용된 비교예 3과 비교예 4의 전방향족 폴리에스테르 수지 펠렛은 하중 변형 온도가 250℃ 이상이나 유동 개시 온도가 300℃ 이상으로 가동이 용이하지 않은 것을 알 수 있다. On the other hand, the amount of the raw material monomer used in the preparation of the wholly aromatic polyester resin is out of the formula 1, the content of the refractive backbone forming monomer is higher than the molar ratio of the hard linear structure forming monomer used in Comparative Examples 1 and 2 It turns out that an aromatic polyester resin pellet has a load deformation temperature less than 250 degreeC. In addition, the wholly aromatic polyester resin pellets of Comparative Example 3 and Comparative Example 4, in which the content of the refractive backbone forming monomer was used at less than 5 mol%, were easily operated with a load deformation temperature of 250 ° C. or higher but a flow start temperature of 300 ° C. or higher. You can see that you did not.
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.
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| JP7210401B2 (en) * | 2019-02-15 | 2023-01-23 | 住友化学株式会社 | Films and laminates |
| US12441879B2 (en) | 2019-08-21 | 2025-10-14 | Ticona Llc | Polymer composition for laser direct structuring |
| US11637365B2 (en) | 2019-08-21 | 2023-04-25 | Ticona Llc | Polymer composition for use in an antenna system |
| US12209164B2 (en) | 2019-09-10 | 2025-01-28 | Ticona Llc | Polymer composition and film for use in 5G applications |
| US12142820B2 (en) | 2019-09-10 | 2024-11-12 | Ticona Llc | 5G system containing a polymer composition |
| US11912817B2 (en) | 2019-09-10 | 2024-02-27 | Ticona Llc | Polymer composition for laser direct structuring |
| US12294185B2 (en) | 2019-09-10 | 2025-05-06 | Ticona Llc | Electrical connector formed from a polymer composition having a low dielectric constant and dissipation factor |
| US11646760B2 (en) | 2019-09-23 | 2023-05-09 | Ticona Llc | RF filter for use at 5G frequencies |
| US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
| WO2021173412A1 (en) | 2020-02-26 | 2021-09-02 | Ticona Llc | Circuit structure |
| US11728559B2 (en) | 2021-02-18 | 2023-08-15 | Ticona Llc | Polymer composition for use in an antenna system |
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| KR100700371B1 (en) * | 2005-11-17 | 2007-03-28 | 삼성정밀화학 주식회사 | High heat resistant wholly aromatic polyester manufacturing method |
| KR20100111094A (en) * | 2009-04-06 | 2010-10-14 | 삼성정밀화학 주식회사 | Wholly aromatic liquid crystalline polyester resin compound with enhanced fluidity and method for preparing the same |
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