WO2020130289A1 - Procédé de préparation d'une composition de résine de mélange de polyéthercétonecétone, et polyéthercétonecétone ainsi préparé - Google Patents

Procédé de préparation d'une composition de résine de mélange de polyéthercétonecétone, et polyéthercétonecétone ainsi préparé Download PDF

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WO2020130289A1
WO2020130289A1 PCT/KR2019/011569 KR2019011569W WO2020130289A1 WO 2020130289 A1 WO2020130289 A1 WO 2020130289A1 KR 2019011569 W KR2019011569 W KR 2019011569W WO 2020130289 A1 WO2020130289 A1 WO 2020130289A1
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ketone
resin composition
polyether ketone
mixed resin
pekk
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Korean (ko)
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정광석
조상현
김재헌
김민성
심유진
안초희
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한화솔루션 주식회사
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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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4087—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group characterised by the catalyst used
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4093—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group characterised by the process or apparatus used
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
    • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK

Definitions

  • the present invention relates to a polyether ketone ketone (Polyether Ketone Ketone, hereinafter also referred to as PEKK) method for preparing a mixed resin composition.
  • PEKK Polyether Ketone Ketone
  • poly phosphite-based compounds are included to improve thermal stability, and as a monomer for the reaction, diphenyl oxide and 1,4-diphenyl benzene are added to improve the crystallization rate of the polymerization reaction and improve the injection molding processability.
  • It relates to a method for producing an ether ketone ketone mixed resin composition and a polyether ketone ketone prepared thereby.
  • Polyether ketone is a generic term for a known industrial resin, and includes polyether ketone, polyether ether ketone, polyether ketone ketone, and a copolymer in which a part of polyether ketone and polyether ketone ketone are mixed.
  • Polyether ketone ketone (PEKK) represented by the following formula is widely used as an engineering plastic because of its high heat resistance and excellent strength.
  • Engineering plastics are used in fields such as automobiles, aircraft, electrical and electronic equipment, and machinery, and their application areas are gradually expanding.
  • the balance of melting temperature and crystallization in the PEKK polymerization process has limitations in the properties and ratios of the monomers. That is, it is quite difficult to improve the injection process by improving the crystallization rate while maintaining the melting temperature of the PEKK resin at an appropriate level.
  • the monomers input to the polymerization reaction of PEKK are polymerized through a Friedel-Crafts Acylation chain reaction.
  • a Friedel-Crafts Acylation chain reaction it is possible to increase the content of the reactants, increase the reaction temperature and time, or increase the amount of the catalyst, but it is possible to have a cost problem, so a method of suppressing oligomer or scale generation is considered.
  • U.S. Patent No. 4,698,393 relates to the preparation of polyarylene ether ketone, to solve the phenomenon of premature precipitation of the polymer and to solve the early inactivation by the complexation of the terminal portion of the polymer chain, phosphite, phosphate, phospho
  • nate, phosphonite, etc. is disclosed, but it is different from the purpose of the present invention.
  • U.S. Patent No. 4,816,556 discloses a copolymer having a specific T/I ratio by adjusting the ratios for terephthaloyl and isophthaloyl halide, lowering the melting point, and further improving processability. Also, the composition and effect of 1,4-diphenoxy benzene have not been disclosed.
  • U.S. Patent No. 9,023,468 relates to a method for preparing a polyetherketone ketone by constructing a repeating unit, in particular, referring to the ratio of isophthaloyl halide and terephthaloyl, bis1,4(4-phenoxy benzoyl )Benzene is disclosed, but there is no mention of diphenyl oxide and mixtures thereof.
  • AlCl 3 is used as a catalyst, a process for removing by-products generated during the reaction and suppressing scale formation is not suggested.
  • PEKK polyether ketone ketone
  • it is stable at high temperature, and at the same time, a process that improves the crystallization rate and thereby improves the formability is required.
  • a process capable of rapidly inhibiting the generation of scale by inhibiting the aggregation of resin particles while simultaneously removing the by-product hydrochloric acid generated during polymerization and minimizing the amount of oligomer produced. Therefore, various developments are needed for PEKK or PEKK mixed resins to overcome the above problems and efficiently obtain high molecular weight resins.
  • Patent Document 1 U.S. Patent No. 4,698,393
  • Patent Document 2 U.S. Patent No. 4,816,556
  • Patent Document 3 U.S. Patent No. 9,023,468
  • the present invention aims to solve all the above-mentioned problems.
  • the present invention aims at minimizing a crosslinking reaction by preventing unnecessary networks caused by radicals occurring locally on or inside the polymer chain by thermal energy.
  • An object of the present invention is to secure thermal stability at a high temperature of a polyether ketone ketone (PEKK) mixed resin, thereby lowering the storage elastic modulus and melt viscosity.
  • PEKK polyether ketone ketone
  • the present invention aims to improve the rate of crystallization of resin in a mold during PEKK resin injection processing by increasing the proportion of ether and terephthaloyl chloride in the repeating unit of the polymer chain of polyether ketone ketone.
  • the object of the present invention is to efficiently remove the by-product hydrochloric acid and obtain a high molecular weight resin by blowing nitrogen gas into the reaction medium in the liquid phase of the polymerization reaction and stirring at the same time.
  • the characteristic configuration of the present invention is as follows.
  • TPC terephthaloyl chloride
  • IPC isophthaloyl chloride
  • PEKK polyether ketone ketone
  • the phosphite (phosphite)-based compound is characterized in that the compound represented by the following formula (1).
  • R1, R2 and R3 are each an aliphatic or aromatic hydrocarbon having a molecular weight of 15 to 1000, and R1, R2 and R3 are characterized by being composed of a hydrocarbon chain composed of an aliphatic or aromatic alone or a hydrocarbon chain composed of an aliphatic or aromatic mixture.
  • the phosphite (phosphite)-based compound is characterized in that the thermal decomposition does not occur at a temperature of 70 °C to 110 °C.
  • the phosphite (phosphite)-based compound is characterized in that contained in 100 to 5000 ppm relative to the pure resin.
  • the 1,4-diphenoxy benzene is characterized in that it further comprises a diphenyl oxide (DPO).
  • DPO diphenyl oxide
  • the 1,4-diphenoxy benzene and diphenyl oxide (DPO) have a weight ratio of 10 to 50:90 to 50.
  • the weight ratio of the terephthaloyl chloride (TPC) and isophthaloyl chloride (IPC) is 7 to 10: 3 to 0.
  • the inert gas is characterized in that at least one or more selected from nitrogen, helium, neon, argon and krypton.
  • a method for preparing a polyether ketone ketone mixed resin composition wherein a nozzle for blowing the inert gas directly into the reaction solution is formed at the top or bottom of the reactor and injected in multiple directions.
  • the agitating step is characterized in that a stirrer having a plurality of agitating blades is rotated to disperse the injected inert gas.
  • the stirrer is provided in at least two or more in the reactor, it is characterized in that to rotate in at least two directions to generate a vortex phenomenon.
  • the reaction solution in step (a) is benzoyl chloride, benzenesulfonyl chloride, 4-chlorobiphenyl, 4-phenoxybenzophenone, 4-(4-phenoxyphenoxy)benzo It characterized in that it comprises at least one capping agent selected from phenone and biphenyl 4-benzenesulfonylphenyl phenyl ether.
  • the temperature of the reaction solution in step (b) is characterized in that -10 to -5 °C.
  • the reactor is heated to 70°C to 110°C while stirring in step (c) to produce polymerized polyether ketone ketone.
  • step (c) the polyether ketone ketone (PEKK) pure resin is washed with methanol (CH 3 OH), hydrochloric acid, and sodium hydroxide (NaOH) solution, and further comprising washing with deionized water (DI water).
  • CH 3 OH methanol
  • hydrochloric acid hydrochloric acid
  • NaOH sodium hydroxide
  • DI water deionized water
  • the reaction medium in the liquid phase is characterized in that it is at least one solvent selected from ortho-dichlorobenzene (oDCB) and dichloromethane.
  • the catalyst is characterized in that it is at least one or more selected from aluminum chloride (AlCl 3 ), potassium carbonate (K 2 CO 3) and iron chloride (FeCl 3 ).
  • a polyether ketone ketone mixed resin composition prepared by the method according to the above production method is provided.
  • a component material manufactured by including the polyether ketone ketone mixed resin composition is provided.
  • a polyether ketone ketone (PEKK) mixed resin composition and a method of manufacturing the same have an effect of securing thermal stability at high temperatures.
  • thermal stability of the PEKK mixed resin is secured by minimizing a crosslinking reaction that prevents unnecessary networks caused by radicals occurring locally in the polymer chain or at the ends of the chain by thermal energy. Accordingly, it provides an effect of lowering the storage modulus and the melt viscosity.
  • the present invention provides an effect of improving the crystallization rate of the mixed resin. Specifically, by increasing the proportion of ether and terephthaloyl chloride in the repeating unit of the polymer chain of polyether ketone ketone, the rate of crystallization of resin or mixed resin in the mold during PEKK resin injection processing is improved, and molding processability during resin injection process It provides the effect of improving.
  • 1 is a graph showing the melt viscosity behavior over time using a Rheometer for the PEKK mixed resin composition according to the present invention.
  • FIG. 2 is a graph showing the storage elastic behavior over time using a Rheometer for the PEKK mixed resin composition according to the present invention.
  • FIG. 3 shows the analysis results of the crystallization rate of polyether ketone ketone (PEKK) prepared according to the present invention.
  • 4 and 5 is a view showing a device capable of simultaneously stirring and flowing nitrogen gas in the reaction solution according to the method for producing a polyether ketone ketone of the present invention.
  • radicals are generated locally in some polymer chains or at the ends of chains at high temperatures, and these radical electrons can bind to adjacent chains.
  • a network is formed in the polymer by the inter-chain bond generated through such a mechanism, it causes an increase in the melt viscosity due to an increase in the storage elastic modulus, and the increased melt viscosity degrades the workability by applying a load to the equipment. It caused the density and apparent quality deterioration.
  • a radical electron generated during high temperature processing by mixing a phosphite-based compound, an oligomer derivative having a phosphite functional group, with a polyetherketone ketone (PEKK) pure resin (neat resin)
  • PEKK polyetherketone ketone
  • polyether ketone ketone mixed resin composition having improved thermal stability, preventing an increase in melt viscosity, and further improving processability.
  • the polyether ketone ketone mixed resin composition Provided is a manufacturing method and a polyether ketone ketone prepared thereby.
  • 1,4-diphenoxy benzene is used as the monomer used in the reaction of the present invention, or diphenyl oxide (DPO) and 1,4-diphenoxy benzene ( 1,4-diphenoxy benzene) to provide the effect of increasing the crystallization rate while maintaining the melting temperature of ordinary PEKK. Accordingly, PEKK polymerization technology with improved injection molding process is proposed.
  • DPO diphenyl oxide
  • 1,4-diphenoxy benzene 1,4-diphenoxy benzene
  • the inert gas is directly blown into the reaction medium in the liquid phase to quickly remove hydrochloric acid (HCl), a by-product generated during the reaction, and at the same time, prevent aggregation of resin particles to suppress scale generation. It provides a method together.
  • (a) 1,4-diphenoxy benzene and 1,4-bis(4-phenoxybenzoyl)benzene (EKKE) selected from the reactor Preparing at least one reaction solution by simultaneously dissolving at least one of terephthaloyl chloride (TPC) and isophthaloyl chloride (IPC) in a liquid phase reaction medium; (b) lowering the temperature of the reaction solution and then adding a catalyst; (c) preparing a pure resin of polyether ketone ketone (PEKK) by blowing and stirring an inert gas directly into the reaction solution after the catalyst is added; And (d) adding a phosphite-based compound to the pure resin to mix it with a mixer, thereby providing a method for producing a polyether ketone ketone mixed resin composition.
  • TPC terephthaloyl chloride
  • IPC isophthaloyl chloride
  • PEKK polyether ketone ketone
  • the phosphite (phosphite)-based compound is characterized in that the compound represented by the following formula (1).
  • R1, R2 and R3 are each an aliphatic or aromatic hydrocarbon having a molecular weight of 15 to 1000, and R1, R2 and R3 are characterized by being composed of a hydrocarbon chain composed of an aliphatic or aromatic alone or a hydrocarbon chain composed of an aliphatic or aromatic mixture.
  • the phosphite (phosphite)-based compound is characterized in that the thermal decomposition does not occur at a temperature of 70 °C to 110 °C. In most commercially available phosphites, thermal decomposition occurs at a temperature of about 70° C. or higher, or heat loss occurs.
  • the phosphite-based compound according to the present invention is a compound having no heat loss at a certain temperature or higher since the phosphite-based compound cannot absorb radicals generated in the PEKK polymer chain when the thermal decomposition occurs below the processing temperature at which the PEKK is processed.
  • the specific temperature is preferably 70 to 110°C.
  • the phosphite-based compound means an oligomer derivative having a phosphite functional group, but is not limited thereto.
  • the phosphite (phosphite)-based compound is characterized in that contained in 100 to 5000 ppm relative to the pure resin.
  • the phosphite-based compound may include 100 to 5000 ppm (part(s) per million), preferably 1000 ppm, relative to the pure resin.
  • the phosphite-based compound When the phosphite-based compound is contained in an amount of less than 100 ppm with respect to the pure resin, it may be difficult to suppress the formation of a network of radical electrons generated at high temperature, and when it is included in excess of 5000 ppm, radicals generated at high temperature Since it is a foreign material that reduces the purity of PEKK pure resin by being injected in an excess amount necessary for absorbing electrons, it causes performance degradation of PEKK's natural mechanical properties, heat resistance, and chemical resistance.
  • Polyether ketone ketone is a polymer produced by chain polymerization of terephthaloyl represented by the following chemical structure 1 and isophthaloyl represented by the following chemical structure 2, and its properties are determined according to the ratio. do.
  • the terephthaloyl moiety has a linear rigidity, and the isophthaloyl moiety gives structural diversity due to its curved structure. Isophthaloyl affects the flexibility, fluidity and crystallization properties of the polymer chain.
  • DPO diphenyl oxide
  • the following chemical structure 4 is a 1,4-diphenoxy benzene structure.
  • the polyether ketone ketone is diphenyl oxide (Diphenyl oxide, DPO) 1,4-diphenoxy benzene having two ether groups having two ether groups (1,4-diphenoxy benzene) alone, or die It is provided to further improve the crystallization rate using a mixture of diphenyl oxide (DPO).
  • DPO diphenyl oxide
  • the 1,4-diphenoxy benzene according to the present invention is characterized in that it further comprises diphenyl oxide (DPO).
  • DPO diphenyl oxide
  • the 1,4-diphenoxy benzene and diphenyl oxide mixture has a weight ratio. It is characterized by 10 to 50: 90 to 50. Preferably a range of 30 to 50:70 to 50 is provided.
  • 1,4-diphenoxy benzene is 10 or less, there is a problem that the effect of increasing the crystallization rate is not clear. Conversely, in the case of 50 or more, there is a problem of a decrease in tensile strength, so the above range is preferable.
  • the terephthaloyl chloride ratio is too high compared to the isophthaloyl chloride, melting is difficult.
  • the ratio of terephthaloyl chloride Isophthaloyl chloride is 10:0, the melting temperature rises to about 400°C, which is difficult to melt, which is disadvantageous in terms of injection processability.
  • a part of the PEKK polymerization monomer (Diphenyl oxide, DPO) is used for the purpose of increasing the crystallization rate while maintaining the melting temperature of the polyether ketone ketone at about 350° C., which is the melting temperature of the conventional polyether ketone ketone.
  • DPO diphenyl oxide
  • the weight ratio of terephthaloyl chloride (TPC) and isophthaloyl chloride (IPC) is 7 to 10: 3 to 0.
  • a 9:1 range is provided.
  • TPC terephthaloyl chloride
  • IPC isophthaloyl chloride
  • the inert gas is characterized in that at least one selected from nitrogen, helium, neon, argon and krypton.
  • the inert gas may be used alone or in combination during the polymerization reaction.
  • a method for preparing a polyether ketone ketone mixed resin composition wherein a nozzle for blowing the inert gas directly into the reaction solution is formed at the top or bottom of the reactor and injected in multiple directions.
  • the agitating step is characterized in that a stirrer having a plurality of stirring blades is rotated to disperse the inert gas, and the stirrer is provided in two or more in the reactor to rotate in at least two directions. Vortex may occur.
  • the rotating shaft of the stirrer may be provided to rotate at a predetermined angle alternately in the forward and reverse directions.
  • the stirring blade is formed to form a predetermined angle with the rotating shaft can increase the dispersion power of the composition in the reactor.
  • FIGS. 4 and 5 According to the method for preparing a polyether ketone ketone of the present invention, a device capable of simultaneously flowing and stirring nitrogen gas in a reaction solution is shown in FIGS. 4 and 5.
  • a nozzle for blowing the inert gas directly into the reaction solution may be formed at the top or bottom of the reactor and injected in multiple directions. This can make the removal of hydrochloric acid by an inert gas more quickly and efficiently.
  • the reaction solution in step (a) is benzoyl chloride, benzenesulfonyl chloride, 4-chlorobiphenyl, 4-phenoxybenzophenone, 4-(4-phenoxyphenoxy)benzo It characterized in that it comprises at least one capping agent selected from phenone and biphenyl 4-benzenesulfonylphenyl phenyl ether.
  • Preferred capping agents include benzoyl chloride, benzenesulfonyl chloride, 4-chlorobiphenyl, 4-phenoxybenzophenone, 4-(4-phenoxyphenoxy)benzophenone, biphenyl 4-benzenesulfonylphenyl phenyl ether, and the like. Can.
  • the temperature of the reaction solution in step (b) is -10 to -5°C.
  • the temperature of the reaction solution is lowered before being input.
  • the temperature may vary depending on the catalyst, but is preferably -10 to -5°C.
  • the reactor is heated to 70°C to 110°C while stirring in step (c) to produce polymerized polyether ketone ketone.
  • the polymerization reaction according to the present invention can be carried out in various reactors, but may preferably be carried out in a continuous agitation reactor (CSTR) or a loop reactor.
  • CSTR continuous agitation reactor
  • step (c) further comprising washing the polyether ketone ketone (PEKK) pure resin with methanol (CH 3 OH), hydrochloric acid and sodium hydroxide (NaOH) solution, and washing three times with deionized water (DI water).
  • the method includes washing with methanol three times, once with hydrochloric acid and sodium hydroxide (NaOH) solution, and washing three times with deionized water (DI water).
  • washing step may further include a step of obtaining a PEKK polymerized resin powder by vacuum drying at 170 to 190 °C.
  • reaction medium of the liquid phase may be at least one or more solvents selected from ortho-dichlorobenzene (oDCB) and dichloromethane, but is not limited thereto, and is usually used as a solvent for Friedel-Crafts Acylation polymerization reaction. If it is used, it is possible.
  • oDCB ortho-dichlorobenzene
  • dichloromethane dichloromethane
  • the catalyst may be at least one selected from aluminum chloride (AlCl 3 ), potassium carbonate (K 2 CO 3 ), and iron chloride (FeCl 3 ), but is not limited thereto, and may be any commonly used catalyst for the Friedel-Crafts Acylation polymerization reaction.
  • the present invention provides a polyether ketone ketone mixed resin composition prepared by the method according to the above production method.
  • it provides a component material produced by including the polyether ketone ketone mixed resin composition.
  • a component material is a vehicle material, an electronic device material, an industrial pipe material, a construction engineering material, a 3D printer material, a textile material, a coating material, a machine tool material, a medical material, an aviation material, a solar material It provides parts materials selected from the group consisting of, battery materials, sports materials, household materials, household materials, and cosmetic materials. However, it is not limited to this.
  • the polyether ketone ketone mixed resin prepared by the above-described manufacturing method shows improved physical properties compared to the polyether ketone ketone and resins prepared through the prior art.
  • the phosphite functional group is bonded to radical electrons generated during high temperature processing to suppress crosslinking of the polymer chain to improve thermal stability, thereby improving processability to prevent an increase in melt viscosity.
  • An improved PEKK mixed resin composition can be obtained.
  • oDCB ortho-dichlorobenzene
  • DPO Diphenyl oxide
  • TPC Terephthaloyl chloride
  • IPC Isophthaloyl chloride
  • Benzoyl chloride as a capping agent in the reactor.
  • the reactor temperature is lowered to -10 to -5 °C.
  • the weight ratio of Terephthaloyl chloride (TPC) and Isophthaloyl chloride (IPC) is 9:1.
  • AlCl 3 as a catalyst is added while maintaining the solution temperature constant at -10 to -5°C. After the catalyst is added, N 2 is blown into the solution and the solution is stirred while the reactor is heated to 100° C. to polymerize PEKK.
  • the polymerized resin was washed with methanol 3 times, 1M hydrochloric acid and 0.5M NaOH solution, washed with DI water 3 times and vacuum dried to obtain PEKK pure resin.
  • a phosphite derivative compound composed of three carbon-oxygen-phosphorus (C-O-P) covalent bonds around the phosphorus (P) atom is introduced into the PEKK pure resin, and then evenly mixed using a mixer to obtain a PEKK mixed resin composition.
  • the mixing ratio of the phosphite derivative compound is 1000 ppm based on PEKK pure resin.
  • the phosphite derivative compound was used as a phosphite derivative compound that does not undergo thermal decomposition at a temperature of 70°C to 110°C.
  • AlCl 3 as a catalyst is added while maintaining the solution temperature constant at -10 to -5°C. After the catalyst is added, N 2 is blown into the solution and the reactor is heated to 100° C. while stirring the solution to polymerize PEKK. The polymerized resin is washed with methanol 3 times, 1M hydrochloric acid and 0.5M NaOH solution and DI water PEKK pure resin was obtained by washing three times and vacuum drying at 180°C.
  • the PEKK polymerized resin according to Example 1 and Comparative Example 1 was used for rheological properties, and the PEKK mixed resin composition of the Example and the PEKK pure resin composition of the Comparative example were subjected to melting viscosity behavior and storage over time during heating at 380°C.
  • the elastic modulus behavior was measured and the results are shown in FIGS. 1 and 2, respectively.
  • As the analysis equipment TA Instruments Co., Ltd., ARES-G2 was used. And the measurement conditions were conducted under a temperature of 380°C, a shear rate of 1 Hz, and a strain of 1.3%.
  • the PEKK polymerization resin according to Example 1 and Comparative Example 1 was measured using DSC to measure the time required for half-crystallization.
  • the measurement method is an isothermal method, in which the heating rate is fixed (10°C/min) and quenched to the crystallization temperature in the state where the polymer is melted (quenching, temperature reduction rate -500°C/min).
  • the rate of crystallization is measured by calculating the time required to reach a certain degree of crystallization through the change.
  • the measuring equipment is DSC 8000 from Perkin Elmer.
  • Example Comparative example Melting temperature (Tm, °C) 350 340 Half-crystallization (210°C standard, second) 62 520
  • Example 1 As described in Table 1, in the case of the PEKK mixed resin composition of Example 1 comprising four monomers (TPC, IPC, DPO, 1,4-diphenoxy benzene) and a phosphite derivative compound according to the present invention, monomer 3 Using the species (TPC, IPC, DPO), it was confirmed that the time required for half-crystallization was reduced by about 1/9 compared to Comparative Example 1 prepared.
  • the PEKK mixed resin composition prepared by including the phosphite derivative of the embodiment according to the present invention has a significantly lower melting viscosity than the PEKK pure resin composition of the comparative example.
  • the PEKK mixed resin composition prepared by including the phosphite derivative of Example 1 according to the present invention has a significantly lower storage elastic modulus than the PEKK pure resin composition of the comparative example.
  • the present invention includes a phosphite derivative compound, and thus has thermal stability of the PEKK mixed resin by minimizing a crosslinking reaction during polymerization. Accordingly, as a result, it provides an effect of lowering the storage modulus and the melt viscosity.
  • the present invention provides an effect of improving the crystallization rate of the mixed resin. Specifically, by increasing the proportion of ether and terephthaloyl chloride in the repeating unit of the polymer chain of polyether ketone ketone, the rate of crystallization of resin or mixed resin in the mold during PEKK resin injection processing is improved, and molding processability during resin injection process It provides the effect of improving.
  • the polyether ketone ketone production method according to the present invention has an effect of minimizing oligomers in resin particles and preventing aggregation of resin particles to suppress scale generation.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyethers (AREA)

Abstract

La présente invention concerne un procédé de préparation d'une composition de résine de mélange de polyéthercétonecétone (ci-après appelé PEKK), et un PEKK préparé selon ce procédé et, spécifiquement, un procédé de préparation d'une composition de résine de mélange de PEKK, qui contient un composé à base de phosphite de façon à présenter une stabilité thermique améliorée, et, simultanément, comprend de l'oxyde de diphényle et du 1,4-diphénylbenzène, qui sont ajoutés en tant que monomères de réaction, de manière à améliorer la vitesse de cristallisation pendant une réaction de polymérisation et à améliorer l'aptitude au moulage par injection; et un PEKK préparé par ce procédé. Selon la présente invention, l'invention concerne un procédé de préparation d'une composition de résine de mélange de PEKK, comprenant les étapes consistant à : (A) mettre en place au moins un élément, choisi parmi le 1,4-diphénoxybenzène et le 1,4-bis (4-phénoxybenzoyl)benzène (EKKE), du chlorure de téréphtaloyle (TPC) et du chlorure d'isophtaloyle (IPC), dans un milieu de réaction liquide dans un réacteur et, simultanément, à dissoudre celui-ci, ce qui permet de préparer une solution de réaction; (b) abaisser la température de la solution de réaction, puis injecter un catalyseur; (c) injecter le catalyseur, puis souffler directement un gaz inerte dans la solution de réaction et l'agiter de manière à préparer une résine pure de PEKK; et (d) injecter un composé à base de phosphite dans la résine pure et le mélanger au moyen d'un mélangeur. Par conséquent, la stabilité thermique Est améliorée pendant le traitement de PEKK et, simultanément, l'aptitude au moulage par injection est améliorée par l'amélioration de la vitesse de cristallisation pendant la réaction de polymérisation.
PCT/KR2019/011569 2018-12-18 2019-09-06 Procédé de préparation d'une composition de résine de mélange de polyéthercétonecétone, et polyéthercétonecétone ainsi préparé WO2020130289A1 (fr)

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US4593061A (en) * 1985-03-29 1986-06-03 Raychem Corporation Stabilized poly(aryl ether ketone) compositions
JPS63159430A (ja) * 1986-12-22 1988-07-02 Mitsubishi Kasei Corp 芳香族ポリ（チオ）エ−テルケトンの製造法
JPS63159431A (ja) * 1986-12-22 1988-07-02 Mitsubishi Kasei Corp 芳香族ポリ（チオ）エ−テルケトンの製造方法
US4874839A (en) * 1988-08-05 1989-10-17 Raychem Corporation Stabilization of poly(arylene ether ketones)
KR20180031735A (ko) * 2015-07-22 2018-03-28 아르끄마 프랑스 폴리(아릴렌-에테르-케톤) (paek) 로부터 제조된 조성물의 안정화 방법

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US4593061A (en) * 1985-03-29 1986-06-03 Raychem Corporation Stabilized poly(aryl ether ketone) compositions
JPS63159430A (ja) * 1986-12-22 1988-07-02 Mitsubishi Kasei Corp 芳香族ポリ（チオ）エ−テルケトンの製造法
JPS63159431A (ja) * 1986-12-22 1988-07-02 Mitsubishi Kasei Corp 芳香族ポリ（チオ）エ−テルケトンの製造方法
US4874839A (en) * 1988-08-05 1989-10-17 Raychem Corporation Stabilization of poly(arylene ether ketones)
KR20180031735A (ko) * 2015-07-22 2018-03-28 아르끄마 프랑스 폴리(아릴렌-에테르-케톤) (paek) 로부터 제조된 조성물의 안정화 방법

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