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EP-4134391-B1 - METHOD FOR PRODUCING POLYETHER KETONE KETONE AND POLYETHER KETONE KETONE PRODUCED THEREBY

EP4134391B1EP 4134391 B1EP4134391 B1EP 4134391B1EP-4134391-B1

Inventors

  • SIM, YU JIN
  • KIM, MIN SUNG
  • KIM, JAE HEON
  • AHN, CHO HEE
  • JEONG, KWANG SEOK
  • CHO, SANG HYUN

Dates

Publication Date
20260506
Application Date
20200409

Claims (10)

  1. A method for producing polyether ketone ketone, which obtains high molecular weight polyether ketone ketone at high yield, the method comprising: (a) preparing a reaction solution by adding at least one selected from diphenyl oxide (DPO) and 1,4-bis(4-phenoxybenzoyl)benzene (EKKE) to terephthaloyl chloride (TPC), isophthaloyl chloride (IPC), and a liquid reaction medium in a reactor and simultaneously dissolving the same; (b) cooling the reaction solution and injecting a catalyst thereto; and (c) after the injecting of the catalyst, directly blowing an inert gas into the reaction solution and stirring the inert gas, characterized in that the catalyst is injected at a rate of 1 to 10 g/min.
  2. The method of claim 1, wherein the catalyst is at least one selected from aluminum chloride (AlCl 3 ), potassium carbonate (K 2 CO 3 ), and iron(III) chloride (FeCl 3 ).
  3. The method of claim 1, wherein a cooling temperature in the step (b) is -10 to -5°C.
  4. The method of claim 1, wherein a nozzle for directly blowing the inert gas into the reaction solution is formed in an upper or lower portion of the reactor, so that the inert gas is injected in multiple directions.
  5. The method of claim 1, wherein the inert gas is at least one selected from nitrogen, helium, neon, argon, and krypton.
  6. The method of claim 1, wherein the step (c) comprises raising the temperature of the reactor to 80 to 100°C while stirring.
  7. The method of claim 1, comprising washing after the step (c) and rinsing with deionized water (DI water).
  8. The method of claim 7, further comprising performing vacuum drying at 170 to 190°C after the rinsing.
  9. The method of claim 1, wherein the reaction solution comprises at least one capping agent selected from benzoyl chloride, benzenesulfonyl chloride, 4-chlorobiphenyl, 4-phenoxybenzophenone, 4-(4-phenoxyphenoxy)benzophenone, and biphenyl 4-benzenesulfonylphenyl phenyl ether.
  10. The method of claim 1, wherein the liquid reaction medium is at least one solvent selected from o-dichlorobenzene (oDCB) and dichloromethane.

Description

TECHNICAL FIELD The present invention relates to a method for producing polyether ketone ketone, and more particularly, to a method for producing polyether ketone ketone and a polyether ketone ketone produced thereby, wherein a catalyst injection rate is controlled during production of the polyether ketone ketone to suppress scale formation, thereby improving the yield thereof. BACKGROUND ART Polyether ketone ketone is a generic term for already known industrial resins, and includes polyether ketone, polyether ether ketone, polyether ketone ketone, and a copolymer in which polyether ketone and polyether ketone ketone are partially mixed. Since polyether ketone ketone (PEKK) represented by the following chemical formula has high heat resistance and excellent strength, PEKK is widely used as engineering plastics. Engineering plastics are used in the fields of automobiles, aircraft, electrical and electronic equipment, machines, and the like, and their field of applications is gradually expanding. As the field of applications of engineering plastics is expanding, the usage environment thereof becomes more severe. Therefore, there is a need for polyether ketone ketone compounds that exhibit more improved physical properties. In addition, there is a need for a producing process with increased yield in order to reduce costs during polymerization reaction. That is, productivity is reduced due to an operational problem in which scale easily occurs during polymerization of PEKK. In this regard, the related art of controlling catalyst injection rates in order to actually increase the yield of polymer resin is known. US Patent Publication No. 4,891,167 discloses that a catalyst is injected at a constant rate, but is limited to polyaryl ether ketone (PAEK), and does not explicitly disclose a relationship between the catalyst injection rate and the yield. Korean Patent Registration No. 0314176 discloses a catalyst injection device for olefin polymerization, which is similar in that a catalyst rate is controlled during polymerization of polymer, but the polymer is limited to polyolefin rather than PEKK. U.S. Patent Publication No. 4,841,013 discloses a method for obtaining a product after polymerization through an additional process of breaking aggregated particles through a pulverization process after polymerization of polyaryl ether ketone (PAEK). However, there is a limitation in that it does not directly describe that the yield is improved through the suppression of scale formation. US Patent No. 9,803,050 discloses a technique for controlling a particle size using a dispersing agent. As non-patent publication, Chemical Engineering Science, (2011) Vol. 66, pp. 1189-1199 discloses that a polymer production rate also increases as a catalyst feed rate increases, but a polymer is disclosed as polypropylene rather than PEKK. WO 2019/098774 A1 discloses a composition which is for treating hair, skin, or fiber and includes a cationic cellulose polymer, wherein the cationic cellulose polymer may be applied to various uses through adjustment of the molecular weight. WO 2020/122366 A1 discloses a process for polymerizing PEKK which has improved resin flowability by post-addition of a capping agent during a polymerization process, and to PEKK polymerized thereby. WO 2020/130289 A1 discloses a method for preparing a polyether ketone ketone (PEKK) mixture resin composition, and a PEKK prepared thereby. US 4 891 167 A discloses crystalline block polymers and chain extended polymers containing blocks of crystalline poly(aryl ether ketones) and a method of producing them. WO 86/06389 A1 discloses crystalline block polymers and chain extended polymers containing blocks of crystalline poly(aryl ether ketones). WO 2011/004164 A2 discloses a method of preparing a poly (ether ketone ketone) consisting essentially of the repeat unit: -Ar-O-Ar-C(=O)-Ar-C(=O)- wherein each Ar is independently an aromatic moiety. GB 2 287 031 A discloses a method of producing polyarylketones by electrophilic substitution using a dispersant for the polymer, wherein the dispersant comprises a polymer having first pendent groups which are substantially compatible with the reaction mixture but are substantially incompatible with the polymer and second pendent groups which comprise Lewis bases. Finally, as non-patent publication, High Perform. Polym. (2014) Vol. 27, pp. 705-713 only discloses that a catalyst is used to produce PEKK and a catalyst feed ratio affects intrinsic viscosity, but does not disclose a catalyst injection rate. Therefore, there is a need to develop a method for producing PEKK, which increases the yield by suppressing scale formation during polymerization of PEKK. [Citation List] (Patent Literature 1) US 4891167(Patent Literature 2) KR 0314176(Patent Literature 3) US 4841013(Patent Literature 4) US 9803050(Non-Patent Literature 1) Chemical Engineering Science, (2011) Vol. 66, pp. 1189-1199(Non-Patent Literature 2) High Perform. Polym. (2014)