WO2023167177A1 - ポリエーテルケトンケトン、及びその製造方法 - Google Patents

ポリエーテルケトンケトン、及びその製造方法 Download PDF

Info

Publication number
WO2023167177A1
WO2023167177A1 PCT/JP2023/007269 JP2023007269W WO2023167177A1 WO 2023167177 A1 WO2023167177 A1 WO 2023167177A1 JP 2023007269 W JP2023007269 W JP 2023007269W WO 2023167177 A1 WO2023167177 A1 WO 2023167177A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon atoms
group
hydrogen
ketone
alkyl group
Prior art date
Application number
PCT/JP2023/007269
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
直樹 齋藤
麗奈 入江
匡志 重信
康史 三木
Original Assignee
株式会社大阪ソーダ
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 株式会社大阪ソーダ filed Critical 株式会社大阪ソーダ
Priority to JP2024504693A priority Critical patent/JPWO2023167177A1/ja
Publication of WO2023167177A1 publication Critical patent/WO2023167177A1/ja

Links

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
    • 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

Definitions

  • the present invention relates to polyether ketone ketone and a method for producing the same.
  • Polyether ketone ketone is a semi-crystalline polymer in which aromatic rings are linked via one ether group and two ketone groups. It is a type of super engineering plastic called polyaryletherketone (PAEK), which has advanced properties and excellent mechanical properties such as abrasion resistance and abrasion resistance. Due to these excellent properties, polyether ketone ketone is widely used as an alternative to existing super engineering plastics and metals in fields such as aircraft applications, automobile applications, electrical and electronic applications, and industrial applications.
  • PAEK polyaryletherketone
  • Non-Patent Document 1 describes that polyether ketone ketone is a semi-crystalline thermoplastic polymer with a high glass transition temperature of 150°C or higher. It is also described that it exhibits a melting point of close to 390° C., and is known to be a material exhibiting a very high melting point among polyaryletherketones.
  • a molding material using polyether ketone ketone for example, in Patent Document 1, a range of about 61:39 to 85:15, preferably a range of 65:35 to 80:20, more preferably about 68:32 15% or A material for shaping semi-crystalline articles using extrusion printing methods comprising producing articles having a weight percent crystallinity of less, preferably 10% or less, and even more preferably 5% or less An additive manufacturing method is described.
  • Polyether ketone ketone has the above-mentioned advanced properties, but on the other hand, it tends to have a higher melting point than other thermoplastic resins. Due to its high melting point, the processing temperature for processing polyetherketoneketone in a molten state, such as injection molding and extrusion molding, is high. A problem is that the processing temperature becomes high when melt-mixing and melt-reacting with the agent.
  • polyether ketone ketone in order to lower the melting point of polyether ketone ketone, a method of mixing a structure having an amorphous part may be taken, but in this case, the crystallinity of the polymer is reduced.
  • Patent Document 2 due to its high crystallinity, polyether ketone ketone is expected to be a material with excellent durability and chemical resistance. It is desired that the material has a degree of hardness.
  • the conventionally known polyether ketone ketone has the problem of a very high melting point and poor workability. Further, in some cases, higher heat resistance than conventionally known polyether ketone ketone is required.
  • an object of the present invention is to provide a polyether ketone ketone that is excellent in at least one of workability and heat resistance, and a method for producing the same.
  • the present invention has the following configurations.
  • R 1 is an aromatic hydrocarbon group having 6 to 24 carbon atoms or an aromatic group having a heteroatom having 4 to 14 carbon atoms
  • R 1 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or an aryl group having 6 to 24 carbon atoms
  • R 2 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a any aryl group
  • R 3 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 24 carbon atoms
  • R 4 is hydrogen, It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms,
  • R 1 is an aromatic hydrocarbon group having 6 to 24 carbon atoms or an aromatic group having a heteroatom having 4 to 14 carbon atoms
  • R 1 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or an aryl group having 6 to 24 carbon atoms
  • R 2 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a any aryl group
  • R 3 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 24 carbon atoms
  • R 4 is hydrogen, It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having
  • Item 3 The polyether ketone ketone according to item 1 or item 2, Crystallinity (calculated from measurement by differential scanning calorimetry) is 10 to 70%.
  • Section 4. A method for producing a polyether ketone ketone represented by formula (A), It is characterized by heating the dichlorodiketone monomer represented by the formula (B) in the presence of a base.
  • [Ar 1 is an aromatic hydrocarbon group having 6 to 24 carbon atoms or an aromatic group having a heteroatom having 4 to 14 carbon atoms
  • R 1 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or an aryl group having 6 to 24 carbon atoms
  • R 2 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a any aryl group
  • R 3 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 24 carbon atoms
  • R 4 is hydrogen, It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 24 carbon atoms
  • n is an integer of 2 or more.
  • R 2 is an aromatic hydrocarbon group having 6 to 24 carbon atoms or an aromatic group having a heteroatom having 4 to 14 carbon atoms
  • R 5 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or an aryl group having 6 to 24 carbon atoms
  • R 6 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or any aryl group
  • R 7 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 24 carbon atoms
  • R 8 is hydrogen, It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 24 carbon atoms
  • Cl means a chlorine atom.
  • the polyether ketone ketone of the present invention is excellent in at least one of workability and heat resistance. According to the polyether ketone ketone according to one embodiment of the present invention, the durability and chemical resistance of polyether ketone ketone are improved, and application to various uses becomes possible. In addition, the polyether ketone ketone according to another embodiment of the present invention maintains a high glass transition temperature even though it has a lower melting point than the conventional polyether ketone ketone, and has good moldability during molding. is good and has excellent heat resistance.
  • the polyether ketone ketone in the present invention is a polyether ketone ketone having a repeating unit represented by formula (A).
  • Ar 1 is an aromatic hydrocarbon group having 6 to 24 carbon atoms or an aromatic group having a heteroatom having 4 to 14 carbon atoms
  • R 1 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or an aryl group having 6 to 24 carbon atoms
  • R 2 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a any aryl group
  • R 3 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 24 carbon atoms
  • R 4 is hydrogen, It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms,
  • Ar 1 is an aromatic hydrocarbon group having 6 to 24 carbon atoms or an aromatic group having a heteroatom having 4 to 14 carbon atoms, preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms. It is a hydrogen group or an aromatic group having a heteroatom of 4 to 8 carbon atoms. Examples of the heteroatom include nitrogen atom, oxygen atom, sulfur atom and phosphorus atom, preferably nitrogen atom and oxygen atom. Ar 1 may have a substituent on the aromatic hydrocarbon group or the aromatic group. In addition, n Ar 1 may be the same or different.
  • Ar 1 examples include a phenylene group, a naphthylene group, a biphenylene group, an indenyl group and an anthraquinolyl group, preferably a phenylene group.
  • R 1 and R 2 , and R 3 and R 4 may be the same or different and are independently hydrogen, an alkyl group having 1 to 12 carbon atoms, It may be either an alkoxy group or an aryl group having 6 to 24 carbon atoms, preferably hydrogen. Also, the combination of n R 1 , R 2 , R 3 and R 4 may be the same or different.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, n- Examples include heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group and the like. Among them, a methyl group is preferred.
  • alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and the like. Among them, a methoxy group is preferred.
  • aryl group examples include a phenyl group and a biphenyl group. Among them, a phenyl group is preferred.
  • n is an integer of 2 or more.
  • the upper limit of n is not particularly limited. A range is more preferred.
  • a polyether ketone ketone having a repeating unit represented by formula (A) is either a homopolymer obtained by polymerizing a single monomer or a copolymer obtained by copolymerizing a plurality of monomers.
  • a copolymer obtained by copolymerizing a plurality of monomers is preferable from the viewpoint of control of physical properties such as the reactivity of polyetherketoneketone during polymerization and the melting point and glass transition temperature of polyetherketoneketone.
  • it may be a homopolymer.
  • a polyether ketone ketone having a repeating unit represented by formula (A) is obtained by polymerization using one or more dichlorodiketone monomers represented by formula (B) described later. is polymerized to form a copolymer, an isomer may be used as the dichlorodiketone monomer represented by the formula (B).
  • dichlorodiketone monomer represented by the formula (B) For example, tere-isomers and iso-isomers can be exemplified, and copolymerization using both tere-isomer and iso-isomer monomers is preferred.
  • the above molar ratio is excellent in terms of heat resistance and moldability during molding.
  • the polyether ketone ketone having a repeating unit represented by formula (A) preferably has a 5% weight loss temperature of 500° C. or higher, more preferably 525° C. or higher, and still more preferably 5% weight loss temperature by thermogravimetric differential thermal analysis. is above 550°C.
  • the polyether ketone ketone having the repeating unit represented by the formula (A) has a 5% weight loss temperature of 500 ° C. or higher by thermogravimetric differential thermal analysis, and is excellent in terms of thermal stability of the polyether ketone ketone. ing.
  • the 5% weight loss temperature by thermogravimetric differential thermal analysis means that the mass of polyetherketoneketone before temperature heating is 100%, and the mass is reduced by 5% from the mass before temperature heating. It means temperature (Td5), for example, the temperature obtained by thermogravimetric measurement of polyetherketoneketone under the following conditions. Using a thermogravimetric differential thermal analyzer, 10 mg of a polyether ketone ketone sample is heated from 30 ° C. at a temperature increase rate of 20 ° C./min in an air or inert gas atmosphere, and the mass before temperature heating is taken as 100%. , the temperature at which the weight becomes 95% is defined as the 5% weight reduction temperature.
  • the polyether ketone ketone having the repeating unit represented by formula (A) preferably has a degree of crystallinity (measured by differential scanning calorimetry) of 10 to 70%.
  • a degree of crystallinity measured by differential scanning calorimetry
  • the degree of crystallinity may be 30% or more, or 45% or more.
  • the polyether ketone ketone having the repeating unit represented by formula (A) is a homopolymer, it tends to have a high degree of crystallinity.
  • a polyether ketone ketone having a higher degree of crystallinity is superior in terms of durability and chemical resistance.
  • the degree of crystallinity may be 10% or more (eg, 10 to 40%) or 15% or more (eg, 15 to 30%).
  • the crystallinity tends to be within the above range.
  • Polyether ketone ketone is excellent in terms of solubility and the like when the degree of crystallinity is low.
  • the degree of crystallinity of polyether ketone ketone can be obtained from the following formula from values measured by differential scanning calorimetry (DSC).
  • the crystallinity of the polyetherketoneketone in the present invention is Preferably, it is about 10% or more, more preferably about 15% or more, even more preferably about 40% or more, and especially preferably about 45% or more, as measured by DSC.
  • the polyether ketone ketone having the repeating unit represented by formula (A) preferably has a glass transition temperature of 140°C or higher, more preferably 150°C or higher. Moreover, the polyether ketone ketone having the repeating unit represented by formula (A) preferably has a melting point of 385° C. or lower, more preferably 380° C. or lower. In particular, the polyether ketone ketone having a repeating unit represented by formula (A) preferably has a glass transition temperature of 140° C. or higher and a melting point of 385° C. or lower, and more preferably has a glass transition temperature of It is 150° C. or higher and has a melting point of 380° C. or lower. When the glass transition temperature and melting point of the polyether ketone ketone having the repeating unit represented by the formula (A) are within the above ranges, the melting temperature during heating is lowered while maintaining heat resistance. Excellent in moldability.
  • the glass transition temperature of polyether ketone ketone can be measured with a thermomechanical analyzer, and the melting point can be measured with a differential scanning calorimeter.
  • the glass transition temperature is obtained by recording a TMA curve while increasing the temperature within a predetermined temperature range, and using the tangent intersection point of the TMA curve as the glass transition temperature.
  • the melting point is the temperature corresponding to the maximum of the melting peak measured by differential scanning calorimetry (DSC).
  • the polyether ketone ketone having a repeating unit represented by formula (A) has a 5% weight loss temperature of 500 ° C. or higher or a glass transition temperature of 140 ° C. or higher by the above-described thermogravimetric differential thermal analysis, and a melting point Any one of 385 ° C. or lower may be satisfied, preferably the 5% weight loss temperature by thermogravimetric differential thermal analysis is 500 ° C. or higher, and the degree of crystallinity (calculated from measurement by differential scanning calorimetry) 10 to 70%, or a glass transition temperature of 140° C. or higher, a melting point of 385° C. or lower, and a crystallinity (calculated by differential scanning calorimetry) of 10 to 70%.
  • thermogravimetric differential thermal analysis It has a 5% weight loss temperature of 500 ° C. or higher by thermogravimetric differential thermal analysis, a glass transition temperature of 140 ° C. or higher, a melting point of 385 ° C. or lower, and a degree of crystallinity (measured by differential scanning calorimetry calculated) may be subordinate to 10-70%.
  • a polyether ketone ketone having a repeating unit represented by formula (A) preferably has a chlorine content of 45 g/kg or less. More preferably 30 g/kg or less, still more preferably 10 g/kg or less.
  • the chlorine content may be 0.01 g/kg or more, 0.1 g/kg or more, 0.5 g/kg or more, or 1 g/kg or more.
  • the chlorine content of polyether ketone ketone is derived from the residual amount of chloride salts and monomers that are by-products of polymerization. If the chlorine content is low, it can be expected to be used in electronic device applications where quality deterioration due to chlorine is a problem. .
  • the chlorine content of polyetherketoneketone can be detected by quantitative analysis using IC (ion chromatography). For example, it can be measured by collecting gas generated by combustion by an automatic combustion device with an absorbing liquid and analyzing the composition of this absorbing liquid with an IC.
  • IC ion chromatography
  • the method for producing the polyetherketoneketone represented by formula (A) in the present invention comprises: It is characterized by heating in the presence of a dichlorodiketone monomer represented by formula (B) and a base.
  • [Ar 1 is an aromatic hydrocarbon group having 6 to 24 carbon atoms or an aromatic group having a heteroatom having 4 to 14 carbon atoms
  • R 1 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or an aryl group having 6 to 24 carbon atoms
  • R 2 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a any aryl group
  • R 3 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 24 carbon atoms
  • R 4 is hydrogen, It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 24 carbon atoms
  • n is an integer of 2 or more.
  • R 2 is an aromatic hydrocarbon group having 6 to 24 carbon atoms or an aromatic group having a heteroatom having 4 to 14 carbon atoms
  • R 5 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or an aryl group having 6 to 24 carbon atoms
  • R 6 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or any aryl group
  • R 7 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 24 carbon atoms
  • R 8 is hydrogen, It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 24 carbon atoms
  • Cl means a chlorine atom.
  • Ar 2 is an aromatic hydrocarbon group having 6 to 24 carbon atoms or an aromatic group having a heteroatom having 4 to 14 carbon atoms, preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms. It is a hydrogen group or an aromatic group having a heteroatom of 4 to 8 carbon atoms. Examples of the heteroatom include nitrogen atom, oxygen atom, sulfur atom and phosphorus atom, preferably oxygen atom and nitrogen atom.
  • Ar 2 is a group corresponding to Ar 1 in formula (1), and may have a substituent on the aromatic hydrocarbon group or the aromatic group.
  • Ar 2 examples include a phenylene group, a naphthylene group, a biphenylene group, an indenyl group and an anthraquinolyl group, preferably a phenylene group.
  • R 5 and R 6 , and R 7 and R 8 may be the same or different and are independently hydrogen, an alkyl group having 1 to 12 carbon atoms, a It may be either an alkoxy group or an aryl group having 6 to 24 carbon atoms, preferably hydrogen.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, n- Examples include heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group and the like. Among them, a methyl group is preferred.
  • alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and the like. Among them, a methoxy group is preferred.
  • aryl group examples include a phenyl group and a biphenyl group. Among them, a phenyl group is preferred.
  • the dichlorodiketone monomer represented by formula (B) can be used without any particular limitation, and for example, a monomer synthesized by the method described in JP-A-2-4732 can be used.
  • a specific example of the dichlorodiketone monomer represented by formula (B) is 1,4-bis(4-chlorobenzoyl)benzene).
  • fluorine-based compounds discharged during polymerization of polyetherketoneketone have a higher environmental load than chlorine-based compounds discharged when dichlorodiketone monomers are used.
  • a catalyst may be used in the production method of the present invention to promote the reaction.
  • the catalyst is not particularly limited, but includes silica-based compounds. Examples include various silicas called silicon dioxide, silicic anhydride, silica, etc., and various mineral compounds containing silica such as silica alumina (aluminum silicate), zeolite, activated clay, sepiolite, montmorillonite, diatomaceous earth, etc. can be done. Among them, silica gel is preferred.
  • the amount of the catalyst used is preferably in the range of 1 g to 100 g, more preferably in the range of 1 g to 50 g, relative to 1 mol of the starting monomer.
  • a co-catalyst may be used in the production method of the present invention.
  • the co-catalyst is not particularly limited, but may be copper powder or a copper compound.
  • copper compounds are preferable, and specific examples of copper compounds include cuprous chloride, cupric chloride, copper (di)acetyl acetate, cuprous acetate, cupric hydroxide, cuprous oxide, cuprous oxide, Cupric, basic cupric carbonate, basic cupric chloride, and the like. These may be in the form containing water of crystallization, or may be used in combination of two or more.
  • the amount of co-catalyst used is preferably in the range of 0.001 to 100 mol parts per 100 mol parts of the raw material monomer, and more preferably in the range of 0.05 to 5 mol parts per 100 mol parts of the raw material monomer. range in mole parts.
  • the base used in the production method of the present invention includes inorganic bases.
  • alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate
  • alkaline earth metal carbonates such as calcium carbonate, strontium carbonate, and barium carbonate
  • lithium hydrogen carbonate and hydrogen carbonate
  • Alkali metal bicarbonates such as sodium, potassium hydrogen carbonate, rubidium hydrogen carbonate and cesium hydrogen carbonate
  • alkaline earth metal bicarbonates such as calcium hydrogen carbonate, strontium hydrogen carbonate and barium hydrogen carbonate can be mentioned.
  • carbonates such as sodium carbonate and potassium carbonate and bicarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate are preferable, and sodium carbonate and potassium carbonate are more preferable. These may be used alone, or two or more of them may be mixed and used without any problem. These bases are preferably used in the form of their anhydrides, but they can also be used as hydrates or aqueous mixtures.
  • aqueous mixture refers to an aqueous solution, a mixture of an aqueous solution and a solid component, or a mixture of water and a solid component.
  • the amount of base in the production method of the present invention depends on the amount of dichlorodiketone monomer.
  • the molar ratio of the base to the total number of moles of chlorine groups in the dichlorodiketone monomer is preferably at least 1 equivalent. Since the base in the present invention can be polymerized without any problem even if it is used in excess, the upper limit is not particularly limited, but the realistic upper limit is 10 equivalents with respect to the total number of moles of chlorine groups in the dichlorodiketone monomer.
  • the molar ratio of the inorganic base to the total number of moles of chlorine groups in the dichlorodiketone monomer represented by formula (B) is 1-2.
  • the organic polar solvent used in the preferred method of polyether ketone ketone polymerization of the present invention is preferably one that does not substantially cause undesirable side reactions such as inhibition of the reaction and decomposition of the polyether ketone ketone produced.
  • organic polar solvents include N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), 1, Nitrogen-containing polar solvents such as 3-dimethyl-2-imidazolidinone (DMI), hexamethylphosphoramide, and tetramethylurea, sulfoxide/sulfone solvents such as dimethylsulfoxide (DMSO), dimethylsulfone, diphenylsulfone, and sulfolane, Examples include nitrile solvents such as benzonitrile, diaryl ethers such as diphenyl ether, ketones such as benzophenone and aceto
  • the amount of the organic polar solvent used is not particularly limited, but it is preferably 10 equivalents or less with respect to the dichlorodiketone monomer represented by formula (B).
  • the amount of the organic polar solvent used is based on the volume of the solvent under normal temperature and normal pressure, and the amount of the organic polar solvent used in the reaction mixture is the amount of the organic polar solvent introduced into the reaction system. It is the amount obtained by subtracting the amount of the organic polar solvent excluded from the reaction system.
  • the production method of the present invention is preferably carried out under a nitrogen atmosphere or under reduced pressure and under heating.
  • the reaction temperature can vary over a wide range, but is carried out at a temperature of at least 200°C or higher, preferably at least 250°C or higher, and at most 400°C, preferably at most 380°C in terms of manufacturability. It is good to be Considering the sublimability and reactivity of the compound used, it is preferable to carry out the reaction while gradually raising the temperature in the range of 250°C to 350°C. Furthermore, it is more preferable to carry out while stirring for the purpose of improving the reactivity.
  • the reaction time in the production method of the present invention can vary widely depending to some extent on the reaction temperature, the properties of the reagents used and the presence of the solvent, but for example 0.1 hour to 100 hours, preferably from the viewpoint of manufacturability. , 0.5 hours to 50 hours.
  • the reaction vessel in the production method of the present invention is not particularly limited as long as it can withstand the above reaction temperature, but a glass vessel or a stainless steel vessel can be used.
  • the pressure applied to the reaction may be any pressure that can maintain the reactants in the liquid phase in the reaction medium, and a pressure in the range of 1 atm to 10 atm can be used, preferably from the viewpoint of productivity. , pressure of 1 to 2 atmospheres.
  • the polymerized polyetherketoneketone can be obtained by separating and recovering from the reaction mixture obtained by the production method described above.
  • the reaction mixture obtained by the above production method contains at least polyether ketone ketone, and may contain other components such as unreacted raw materials, by-product salts, unreacted bases, catalysts and solvents.
  • the method for recovering the polyether ketone ketone from such a reaction mixture is not particularly limited. and a method of removing the residual solvent under reduced pressure.
  • solvents with such characteristics are generally It is a solvent with a relatively high polarity, and the preferred solvent differs depending on the type of raw materials and by-product salts used, so it cannot be limited. Examples include water, methanol, ethanol, propanol, isopropanol, butanol, and hexanol.
  • An aqueous sodium solution, an aqueous potassium hydroxide solution, an aqueous sodium carbonate solution, and an aqueous potassium carbonate solution are preferred, and acetone, water, hydrochloric acid, and an aqueous sodium hydroxide solution are more preferred.
  • the method of removing the residual solvent under reduced pressure it may be carried out under heating, if necessary, in the range of 0.001 to 1 atm after the completion of the reaction.
  • the structure of the polyether ketone ketone in the present invention can be confirmed by infrared spectroscopy or nuclear magnetic resonance spectroscopy.
  • the polyether ketone ketone in the present invention can be suitably used as an engineering plastic because it has excellent heat resistance, chemical resistance, and durability.
  • it can be suitably used as an engineering plastic in the fields of automobiles/aircraft, electrical/electronic equipment, machinery, and other fields (medical/nursing equipment, heat-resistant sheets, heat-resistant fibers, etc.).
  • applications in the fields of automobiles and aircraft include, for example, engine covers, intake manifolds, door mirror stays, accelerator pedals, arm rests, seat belt parts, door handles, cooling fans, and the like.
  • Applications in the field of electrical and electronic equipment include, for example, gears, hubs, connectors, motor brackets, various plugs, and crimp terminals.
  • Applications in the mechanical field include, for example, bearings, bearing retainers, gears, fans, casters and the like.
  • Applications in the medical field include implant materials and artificial bones. Other uses include materials for 3D printers and the like.
  • Example 1 Polymerization of polyether ketone ketone 1 To a 100-mL three-necked flask, 10.06 g of white powder 1,4-bis(4-chlorobenzoyl)benzene (tere-isomer), 3.42 g of sodium carbonate, copper oxide (I ), 0.65 g of silica gel (AEROSIL (registered trademark) 300), and 14.15 g of diphenyl sulfone were charged, the inside of the flask was degassed under reduced pressure, and the inside of the system was replaced with an inert gas. The temperature was raised to 200° C., degassing was performed again under reduced pressure, and the inside of the system was replaced with an inert gas.
  • AEROSIL registered trademark
  • the temperature was raised to 280° C. under an inert gas to start aging.
  • the reaction time was 2 hours at 280° C., 1 hour at 300° C., and 2 hours at 320° C.
  • the mixture was cooled to room temperature.
  • a portion of the reaction crude product was sampled and subjected to 1 H-NMR measurement.
  • ion-exchanged water was added, and the reaction crude product was taken out from the inside of the flask while being pulverized.
  • the reaction crude product was collected by filtration, pulverized into granules in a mortar, and washed with acetone and ion-exchanged water.
  • Example 2 Polymerization of polyether ketone ketone 2 To a 100 mL three-necked flask, 14.0 g of white powdery 1,4-bis(4-chlorobenzoyl)benzene (tele-isomer), white powdery 1,3-bis(4 -Chlorobenzoyl)benzene (iso) 6.0 g, sodium carbonate 6.66 g, copper (I) oxide 0.0344 g, silica gel (AEROSIL (registered trademark) 300) 1.38 g, diphenyl sulfone 28.18 g were charged, and a flask was The inside was degassed under reduced pressure, and the inside of the system was replaced with an inert gas.
  • AEROSIL registered trademark
  • tele isomer:iso isomer (molar ratio) was 70:30.
  • the temperature was raised to 200° C., degassing was performed again under reduced pressure, and the inside of the system was replaced with an inert gas.
  • the temperature was raised to 280° C. under an inert gas to start aging.
  • the reaction time was 2 hours at 280° C., 1 hour at 300° C., and 2 hours at 320° C. After aging at each reaction temperature, the mixture was cooled to room temperature.
  • reaction crude product was sampled and 1 H-NMR was measured, and peaks derived from 1,4-bis(4-chlorobenzoyl)benzene and 1,3-bis(4-chlorobenzoyl)benzene decreased. Therefore, the reaction was terminated. After cooling, ion-exchanged water was added, and the reaction crude product was taken out from the inside of the flask while being pulverized. The reaction crude product was collected by filtration, pulverized into granules in a mortar, and washed with acetone and ion-exchanged water.
  • the temperature was raised to 280° C. under an inert gas to start aging.
  • the reaction time was 2 hours at 280° C., 1 hour at 300° C., and 2 hours at 320° C.
  • the mixture was cooled to room temperature.
  • a portion of the reaction crude product was sampled and subjected to 1 H-NMR measurement.
  • ion-exchanged water was added, and the reaction crude product was taken out from the inside of the flask while being pulverized.
  • the reaction crude product was collected by filtration, pulverized into granules in a mortar, and washed with acetone and ion-exchanged water.
  • the 1 H-NMR measurement was carried out by using a measuring apparatus manufactured by JEOL Ltd. (JNM-ECZ400S), using hexamethyldisiloxane as a standard substance, and dissolving 10 mg of a sample in bisulfuric acid.
  • the glass transition temperature was measured by thermomechanical analysis using a circular test piece with a thickness of 1 mm and a diameter of 10 mm. Specifically, using Netsch's (TMA 4000 SE) as a measuring device, under the conditions of a load of 10 g and a temperature increase rate of 5 ° C./min in an air atmosphere, measurement is performed by compression at a temperature in the range of 25 to 200 ° C. Ta. The tangent intersection point of the curve at 100 to 180° C. on the obtained chart was taken as the glass transition temperature.
  • TMA 4000 SE Netsch's
  • ⁇ Melting point measurement> Melting point measurements were determined by differential scanning calorimetry (DSC) measurements. Specifically, the melting point was measured using a measuring device (DSC3+) manufactured by METTLER TOLEDO, and the thermal properties were measured in a nitrogen atmosphere. Using the following measurement conditions, the value of the endothermic peak in Second Run was taken as the melting point. (First Run) ⁇ Temperature increase from 50°C to 400°C, temperature increase rate 10°C/min ⁇ After temperature increase, temperature decrease to 50°C, temperature decrease rate 320°C/min (Second Run) ⁇ Temperature rise from 50°C to 400°C, heating rate 10°C/min
  • Chlorine content in the polymer was detected by quantitative analysis using IC (ion chromatography). Specifically, the sample was placed in a ceramic boat and weighed, then burned using an automatic sample burner, and the generated gas was captured in 15 mL of the absorbent. Quantitative analysis by IC was performed on a liquid obtained by adding ultrapure water to a constant volume of 50 mL. As a measuring device, an automatic combustion device (manufactured by Mitsubishi Chemical Analytic Tech, AQF-100) and IC (manufactured by Thermo Fisher Scientific, ICS-5000+) are used, and the chlorine content (g / kg) in the polymer is measured. quantified.
  • IC ion chromatography
  • polyether ketone ketone 1 (Example 1) and polyether ketone ketone 2 (Example 2) obtained from a dichlorodiketone monomer had a glass transition temperature and a It has high heat resistance as indicated by the 5% weight loss temperature.
  • the melting point is lower than 390° C. in all cases, and polyetherketoneketone 2 (Example 2) in particular has a relatively low melting point and is expected to exhibit good workability.
  • the chlorine content both polyether ketone ketone 1 (Example 1) and polyether ketone ketone 2 (Example 2) show low values. The amount is likely to be small, and it is expected to be used in electronic device applications where low chlorine content is required.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)
PCT/JP2023/007269 2022-03-02 2023-02-28 ポリエーテルケトンケトン、及びその製造方法 WO2023167177A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2024504693A JPWO2023167177A1 (enrdf_load_stackoverflow) 2022-03-02 2023-02-28

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2022-031358 2022-03-02
JP2022031358 2022-03-02
JP2022140051 2022-09-02
JP2022-140051 2022-09-02

Publications (1)

Publication Number Publication Date
WO2023167177A1 true WO2023167177A1 (ja) 2023-09-07

Family

ID=87883766

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/007269 WO2023167177A1 (ja) 2022-03-02 2023-02-28 ポリエーテルケトンケトン、及びその製造方法

Country Status (2)

Country Link
JP (1) JPWO2023167177A1 (enrdf_load_stackoverflow)
WO (1) WO2023167177A1 (enrdf_load_stackoverflow)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63258923A (ja) * 1987-04-16 1988-10-26 Asahi Chem Ind Co Ltd 芳香族ポリエ−テルケトンの製造方法
JPS6465130A (en) * 1987-09-04 1989-03-10 Asahi Chemical Ind Aromatic polyether-ketone and its production
JPH03215524A (ja) * 1990-01-19 1991-09-20 Idemitsu Kosan Co Ltd ポリエーテルケトン系共重合体およびその製造方法
JPH05295104A (ja) * 1992-04-20 1993-11-09 Idemitsu Kosan Co Ltd 芳香族ポリエーテルケトン共重合体及びその製造方法
US20200406595A1 (en) * 2018-03-13 2020-12-31 Arkema Inc. Film laminates based on polyaryletherketones

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63258923A (ja) * 1987-04-16 1988-10-26 Asahi Chem Ind Co Ltd 芳香族ポリエ−テルケトンの製造方法
JPS6465130A (en) * 1987-09-04 1989-03-10 Asahi Chemical Ind Aromatic polyether-ketone and its production
JPH03215524A (ja) * 1990-01-19 1991-09-20 Idemitsu Kosan Co Ltd ポリエーテルケトン系共重合体およびその製造方法
JPH05295104A (ja) * 1992-04-20 1993-11-09 Idemitsu Kosan Co Ltd 芳香族ポリエーテルケトン共重合体及びその製造方法
US20200406595A1 (en) * 2018-03-13 2020-12-31 Arkema Inc. Film laminates based on polyaryletherketones

Also Published As

Publication number Publication date
JPWO2023167177A1 (enrdf_load_stackoverflow) 2023-09-07

Similar Documents

Publication Publication Date Title
US8735532B2 (en) Synthesis of and curing additives for phthalonitriles
US8981036B2 (en) Synthesis of and curing additives for phthalonitriles
US8859712B2 (en) Synthesis of and curing additives for phthalonitriles
WO2021241492A1 (ja) 結晶性ポリエーテルニトリル
JP2010095614A (ja) ポリエーテルエーテルケトンの製法
WO2023167177A1 (ja) ポリエーテルケトンケトン、及びその製造方法
JP2022071959A (ja) ポリエーテルニトリル
KR102057205B1 (ko) 폴리아릴에테르케톤 및 이의 제조 방법
TWI853070B (zh) 樹脂原料用組成物
WO2015183518A1 (en) Synthesis of and curing additives for phthalonitriles
JP2010248414A (ja) ポリフェニレンエーテル共重合体及びその製造方法
JP7240935B2 (ja) ポリビフェニルエーテルスルホン樹脂及びその製造方法並びに成形品
JP2021050315A (ja) 反応性ポリアリールエーテルケトン
JPS59164326A (ja) 芳香族ポリエ−テルケトン系共重合体
WO1991013929A1 (fr) Polymeres non cristallins et leur production
JPH01259030A (ja) 芳香族ポリエーテルケトン共重合体
JP2551455B2 (ja) 新規芳香族ポリスルホン及びその製造方法
JPH0456047B2 (enrdf_load_stackoverflow)
JPS59136326A (ja) ポリエ−テルスルホンの製造方法
JPH01259029A (ja) 芳香族ポリエーテルケトン
JP2025102281A (ja) 多官能ビニル化合物、その組成物、及び硬化物
JPH0428733B2 (enrdf_load_stackoverflow)
JPH0237933B2 (ja) Hokozokuhorieeterukeijugotaioyobisonoseizohoho
JPS61159421A (ja) 芳香族ポリエ−テル系重合体
JPH05178983A (ja) 芳香族ポリエーテルケトンの製造方法

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: 23763434

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2024504693

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 23763434

Country of ref document: EP

Kind code of ref document: A1