[go: up one dir, main page]

WO2017091049A1 - Procédé de préparation de résine de polyester totalement aromatique et résine de polyester totalement aromatique ainsi préparée - Google Patents

Procédé de préparation de résine de polyester totalement aromatique et résine de polyester totalement aromatique ainsi préparée Download PDF

Info

Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
aromatic polyester
wholly aromatic
polyester resin
polycondensation
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2016/013783
Other languages
English (en)
Korean (ko)
Inventor
장선화
송부섭
이진규
이윤응
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Seyang Polymer Corp
Original Assignee
Seyang Polymer Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Seyang Polymer Corp filed Critical Seyang Polymer Corp
Publication of WO2017091049A1 publication Critical patent/WO2017091049A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/127—Acids containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/133—Hydroxy compounds containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne un procédé de préparation d'une résine de polyester totalement aromatique. Dans le procédé de préparation d'une résine de polyester totalement aromatique par une réaction de polycondensation à une échelle de production en masse, une réaction de polycondensation est effectuée de sorte que le rapport molaire des monomères bruts initialement fournis est maintenu en minimisant la sortie des monomères et des monomères acétylés, qui ne participent pas à la réaction de polycondensation, conjointement avec l'acide acétique gazeux à une température élevée, et ainsi, les propriétés physiques de la résine de polyester totalement aromatique finalement préparée peuvent être égalisées. En outre, la résine de polyester totalement aromatique préparée selon l'invention présente des propriétés physiques souhaitées, qui sont exprimées de manière égale pour les lots respectifs, et ainsi, permet d'améliorer la fiabilité des pièces automobiles, des pièces électriques et électroniques, des articles de petite taille moulés avec précision, et analogues, qui sont fabriqués par moulage de la résine de polyester totalement aromatique.
PCT/KR2016/013783 2015-11-26 2016-11-28 Procédé de préparation de résine de polyester totalement aromatique et résine de polyester totalement aromatique ainsi préparée Ceased WO2017091049A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2015-0166384 2015-11-26
KR1020150166384A KR20170073745A (ko) 2015-11-26 2015-11-26 전방향족 폴리에스테르 수지의 제조방법 및 이에 따라 제조된 전방향족 폴리에스테르 수지

Publications (1)

Publication Number Publication Date
WO2017091049A1 true WO2017091049A1 (fr) 2017-06-01

Family

ID=58764183

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2016/013783 Ceased WO2017091049A1 (fr) 2015-11-26 2016-11-28 Procédé de préparation de résine de polyester totalement aromatique et résine de polyester totalement aromatique ainsi préparée

Country Status (2)

Country Link
KR (1) KR20170073745A (fr)
WO (1) WO2017091049A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102617546B1 (ko) * 2023-03-29 2023-12-28 주식회사 프로팩 생분해성 고분자 수지 제조공정시스템

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010132828A (ja) * 2008-12-08 2010-06-17 Hitachi Plant Technologies Ltd ポリエステルの合成装置および合成方法
KR20110004282A (ko) * 2009-07-06 2011-01-13 스미또모 가가꾸 가부시끼가이샤 액정 폴리에스테르의 제조 방법
JP2011184583A (ja) * 2010-03-09 2011-09-22 Aica Kogyo Co Ltd 結晶性不飽和ポリエステル及び硬化性組成物
KR20130001686A (ko) * 2011-06-27 2013-01-04 스미또모 가가꾸 가부시끼가이샤 액정 폴리에스테르의 제조 방법
KR20150072948A (ko) * 2013-12-20 2015-06-30 심천 워트 어드밴스드 머티리얼즈 주식회사 방향족 액정 폴리에스테르 수지의 제조방법 및 방향족 액정 폴리에스테르 수지 컴파운드의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010132828A (ja) * 2008-12-08 2010-06-17 Hitachi Plant Technologies Ltd ポリエステルの合成装置および合成方法
KR20110004282A (ko) * 2009-07-06 2011-01-13 스미또모 가가꾸 가부시끼가이샤 액정 폴리에스테르의 제조 방법
JP2011184583A (ja) * 2010-03-09 2011-09-22 Aica Kogyo Co Ltd 結晶性不飽和ポリエステル及び硬化性組成物
KR20130001686A (ko) * 2011-06-27 2013-01-04 스미또모 가가꾸 가부시끼가이샤 액정 폴리에스테르의 제조 방법
KR20150072948A (ko) * 2013-12-20 2015-06-30 심천 워트 어드밴스드 머티리얼즈 주식회사 방향족 액정 폴리에스테르 수지의 제조방법 및 방향족 액정 폴리에스테르 수지 컴파운드의 제조방법

Also Published As

Publication number Publication date
KR20170073745A (ko) 2017-06-29

Similar Documents

Publication Publication Date Title
WO2012067396A2 (fr) Composé de résine polyester cristalline liquide entièrement aromatique ayant une aptitude améliorée à l'écoulement
WO2017082710A1 (fr) Procédé de production d'une résine de polyester entièrement aromatique présentant une aptitude améliorée à l'écoulement, et polyester entièrement aromatique produit à partir de cette dernière
WO2013066003A1 (fr) Composé de résine de polyester entièrement aromatique à cristaux liquides et produit doté de propriétés antistatiques
WO2011043634A2 (fr) Composé de résine à base d'un polyester cristal liquide entièrement aromatique ayant une résistance à la chaleur améliorée, et son procédé de préparation
KR20250150171A (ko) 전방향족 폴리에스테르 및 폴리에스테르 수지 조성물
WO2020111619A1 (fr) Procédé permettant de produire des fibres de polyester cristallin liquide entièrement aromatique ayant des propriétés de filage améliorées
WO2012105770A2 (fr) Composition de résine de polyester et son procédé de production
WO2012070774A2 (fr) Procédé de préparation d'une résine de polyester amide cristal liquide totalement aromatique et procédé de préparation d'un mélange à base de résine de polyester amide cristal liquide totalement aromatique
WO2012138033A1 (fr) Matériau composite polymère thermiquement conducteur et objet le comprenant
KR102873607B1 (ko) 폴리에스테르 필름 및 이의 제조방법
EP2443168A2 (fr) Procédés de préparation d'une résine polyester cristalline liquide entièrement aromatique et mélange à base de résine polyester cristalline liquide entièrement aromatique présentant une viscosité constante à l'état fondu
JP2001139674A (ja) 液晶性ポリエステルの製造方法
EP2660265B1 (fr) Polyester à cristaux liquides et son procédé de préparation
WO2017091049A1 (fr) Procédé de préparation de résine de polyester totalement aromatique et résine de polyester totalement aromatique ainsi préparée
WO2011087263A2 (fr) Procédé de fabrication d'une résine de polyester cristalline liquide entièrement aromatique, résine de polyester cristalline liquide entièrement aromatique fabriquée par le procédé et composé de la résine de polyester cristalline liquide entièrement aromatique
CN104974337A (zh) 一种可降解支化聚酯及其制备方法
CN117164909B (zh) 一种熔体直拉耐候太阳能背板基膜的制备方法
WO2013066008A1 (fr) Composition de résine de polyester à cristaux liquides entièrement aromatique qui présente une meilleure résistance au cloquage
CN114957976B (zh) 一种高性能低介电的pa6复合材料及其制备方法
CN114181391B (zh) 热塑性聚酰亚胺树脂及其制备方法
WO2017111261A1 (fr) Procédé de préparation d'une résine de polyester biodégradable, et résine de polyester biodégradable préparée par procédé
KR101049259B1 (ko) 고점도 폴리에스테르 수지의 제조 방법
KR102196124B1 (ko) 열가소성 폴리에스테르계 엘라스토머의 제조방법 및 폴리에스테르계 수지의 글리콜리시스 방법
WO2015030446A1 (fr) Procédé de préparation d'une résine polyester biodégradable
KR960006302B1 (ko) 고중합도 폴리에스테르의 제조방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16868945

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16868945

Country of ref document: EP

Kind code of ref document: A1