Polyketones and methods for producing polyketones

Abstract

To provide a novel polyketone. [Solution] A polyketone having a constituent unit represented by formula (A) (wherein p represents an integer between 2 and 8; R 1 R represents an aromatic hydrocarbon group having 6 to 24 carbon atoms, which may have substituents, or an aromatic heterocyclic group having 4 to 24 carbon atoms, which may have substituents; multiple R 1 (These can be identical or different from each other; q represents an integer between 0 and 3, inclusive.) TIFF2026110002000024.tif30170

Description

[Technical Field]

[0001] This disclosure relates to polyketones and methods for producing polyketones. [Background technology]

[0002] Polyketones, particularly aromatic polyetherketones (PAEKs), are a type of super engineering plastic that possesses excellent properties such as heat resistance, oil resistance, chemical resistance, abrasion resistance, and flame retardancy, and are therefore widely used in fields such as automobiles, aerospace, medical materials, and electronic materials. Conventional PAEKs mostly consist of repeating units that link a benzene ring, an ether bond, and a carbonyl group (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2023-095966 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] It is believed that introducing a new structure to a polyketone can impart unprecedented properties to it. Therefore, the objective of this disclosure is to provide a novel polyketone. [Means for solving the problem]

[0005] The inventors of this disclosure, after diligent study, have solved the above problem by introducing an oligofuran skeleton into polyketones, and have completed this disclosure. In other words, this disclosure includes the following:

[0006] [1] A polyketone having a constituent unit represented by formula (A). [ka] (In the formula, p represents an integer of 2 or more and 8 or less; R , , , , , , , , represents an aromatic hydrocarbon group having 6 to 24 carbon atoms which may have a substituent or an aromatic heterocyclic group having 4 to 24 carbon atoms which may have a substituent; a plurality of R 1 may be the same or different from each other; q represents an integer of 0 or more and 3 or less.) [2] The polyketone according to [1], wherein the R 1 is an aromatic hydrocarbon group having 6 to 24 carbon atoms which may have a substituent, and the q is 0 or 1. [3] The polyketone according to [1] or [2], wherein the p is 2 or 4. [4] A plastic molded article containing the polyketone according to any one of [1] to [3].[[]END]] [5] The plastic molded article according to [4], which is a sliding member, a pipe, a composite, a resin laminate, a powder coating film, a film, or a medical part. [6] A polyketone composition containing the polyketone according to any one of [1] to [3].[[]END]] [7] The polyketone composition according to [6], which is a resin composition for 3D printing. [8] The polyketone composition according to [6], further containing a solvent and the polyketone dissolved in the solvent. [9] The polyketone composition according to [8], which is used for a paint, an adhesive, a tackifier, or an ink.

[10] A pH indicator containing the polyketone according to any one of [1] to [3].[[]END]]

[11] A method for producing a polyketone, which includes a reaction step of reacting an acid halide with an aromatic hydrocarbon in the presence of a Lewis acid, where the acid halide includes an acid halide represented by the formula (a1), A method for producing a polyketone, wherein the aromatic hydrocarbon contains an aromatic compound represented by formula (a2).

Chemical formula

Advantages of the Invention

[0007] According to the present disclosure, a novel polyketone, more specifically, a novel polyketone having an oligofuran skeleton can be provided.

Brief Description of the Drawings

[0008] [Figure 1] 1H NMR spectra of the polyketones obtained in Examples 1 to 4 and Comparative Example 2. [Figure 2] IR spectra of the polyketones obtained in Examples 1 to 4 and Comparative Examples 1 to 2. [Figure 3] MALDI-TOF MS spectrum of the polyketone obtained in Example 1. [Figure 4] Thermogravimetric analysis (TGA) curves of the polyketones obtained in Examples 1 to 4 and Comparative Examples 1 to 2. [Figure 5]The storage modulus and tanδ of the polyketones obtained in Examples 1-4 and Comparative Examples 1-2 were determined by dynamic viscoelasticity measurement (DMA). [Figure 6] These are the ultraviolet-visible absorption spectra and fluorescence spectra measured after dissolving the polyketone obtained in Example 1 in trifluoroacetic acid, hexafluoroisopropanol, and formic acid, respectively. [Figure 7] These are the ultraviolet-visible absorption spectra and fluorescence spectra of the polyketones obtained in Examples 1-4 and Comparative Example 2. [Figure 8] These are the ultraviolet-visible absorption spectra and fluorescence spectra of the polyketones obtained in the solid state in Examples 1-4 and Comparative Examples 1-2. [Figure 9] These are the ultraviolet-visible absorption spectra and fluorescence spectra of the polyketone solid film obtained in Example 1, as well as its base-treated film and base-acid treated film. [Modes for carrying out the invention]

[0009] The following is a detailed description of this disclosure. However, the following description of the constituent elements is merely one example (representative example) of an embodiment of this disclosure, and this disclosure is not limited to these contents. It can be implemented in various modified forms within the scope of its essence.

[0010] In this disclosure, "X~Y" indicating a range means "X or greater and Y or less". Furthermore, when numerical ranges expressed as "X~Y" or "X or greater and Y or less" are listed in stages (for example, in preferred order), the upper and lower limits of each numerical range can be any combination.

[0011] In this disclosure, any mention of "X such as x1, x2, and x3" is merely an example of X, and does not imply that X is limited to x1, x2, and x3.

[0012] 1. Polyketones The polyketone according to an embodiment of the present disclosure has a structural unit represented by formula (A). That is, the polyketone according to this embodiment has an oligofuran skeleton. The polyketone according to this embodiment may have only one kind of structural unit represented by formula (A), or may have two or more kinds. The structural unit represented by formula (A) is preferably a repeating unit contained in the main chain of the polyketone.

[0013]

Chemical formula

[0014] p represents an integer of 2 or more and 8 or less, preferably an integer of 2 or more and 4 or less, more preferably 2 or 4, and still more preferably 2. That is, the polyketone according to this embodiment has a bifuran skeleton, a terfuran skeleton, or a quarterfuran skeleton, preferably has a bifuran skeleton or a quarterfuran skeleton, and more preferably has a bifuran skeleton.

[0015] R 1 represents an aromatic hydrocarbon group having 6 or more and 24 or less carbon atoms which may have a substituent or an aromatic heterocyclic group having 4 or more and 24 or less carbon atoms which may have a substituent. R 1 is preferably an unsubstituted aromatic hydrocarbon group having 6 or more and 24 or less carbon atoms. A plurality of R 1 may be the same or each other may be different.

[0016] In the present disclosure, the aromatic hydrocarbon may be monocyclic, polycyclic, or condensed cyclic. Also, in the present disclosure, the number indicating the number of carbon atoms of the hydrocarbon group does not include the number of carbon atoms of the substituent.

[0017] Furthermore, when this disclosure refers to groups in polyketones and monomers that serve as raw materials for polyketones as "may have substituents," the substituents can be appropriately selected depending on the desired polyketone. Also, the positions and number of substituents are not particularly limited. Examples of substituents include, specifically, deuterium atoms; alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl groups; cycloalkyl groups having 3 to 6 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups; aromatic hydrocarbon groups having 6 to 10 carbon atoms such as phenyl, 1-naphthyl, and 2-naphthyl groups; alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butoxy, sec-butoxy, iso-butoxy, and tert-butoxy groups; and inert silyl groups such as trimethylsilyl, triethylsilyl, and triphenylsilyl groups.

[0018] R 1 The number of carbon atoms in the aromatic hydrocarbon group represented is preferably 6 to 20, more preferably 6 to 16, and even more preferably 6 to 12.

[0019] R 1 The aromatic hydrocarbon group represented by is a divalent group obtained by removing two arbitrary hydrogen atoms directly bonded to the aromatic ring from an aromatic hydrocarbon having 6 to 24 carbon atoms. 1Aromatic hydrocarbon groups having 6 to 24 carbon atoms represented by include, specifically, divalent groups obtained by removing two arbitrary hydrogen atoms directly bonded to the aromatic ring of benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, triphenylene, or perylene. Preferably, these are divalent groups obtained by removing two arbitrary hydrogen atoms directly bonded to the aromatic ring of benzene or naphthalene (i.e., phenylene groups or naphthalene diyl groups), more preferably 1,4-phenylene groups, 1,2-phenylene groups, 1,2-naphthalene diyl groups, 1,4-naphthalene diyl groups, 1,8-naphthalene diyl groups, 2,3-naphthalene diyl groups, 2,6-naphthalene diyl groups, or 2,7-naphthalene diyl groups, and even more preferably 1,4-phenylene groups or 2,6-naphthalene diyl groups.

[0020] R 1 The number of carbon atoms in the aromatic heterocyclic group represented by is preferably 4 to 20, more preferably 4 to 16, even more preferably 4 to 12, and even more preferably 4 or 5. The heteroatoms in the heterocycle of the aromatic heterocyclic group are preferably oxygen atoms, nitrogen atoms, or sulfur atoms, more preferably oxygen atoms or sulfur atoms, and even more preferably oxygen atoms.

[0021] R 1 The aromatic heterocyclic group represented by is a divalent group obtained by removing two arbitrary hydrogen atoms directly bonded to the aromatic ring from an aromatic heterocyclic ring with 4 to 24 carbon atoms. 1 The aromatic heterocyclic group having 4 to 24 carbon atoms represented by can be specifically a divalent group having two arbitrary hydrogen atoms removed from furan, thiophene, pyrrole, or pyridine, preferably a divalent group having two arbitrary hydrogen atoms removed from furan (i.e., a franziyl group), and more preferably a 2,5-franziyl group.

[0022] q represents an integer between 0 and 3, preferably between 0 and 2, and more preferably 0 or 1. When q is 1, the polyketone having the constituent units represented by formula (A) is polyetherketone ketone (PEKK).

[0023] In summary, the following constituent units are preferred as constituent units represented by formula (A).

[0024] [ka]

[0025] In the polyketone according to this embodiment, the content of the constituent unit represented by formula (A) is preferably 20 mol% to 100 mol%, more preferably 50 mol% to 95 mol%, even more preferably 70 mol% to 90 mol%, and even more preferably 80 mol% to 85 mol%, in order to fully exhibit the properties derived from the oligofuran skeleton. Alternatively, for the same reasons as above, the content of the constituent unit represented by formula (A) is preferably 20% by mass to 100% by mass, more preferably 50% by mass to 95% by mass, even more preferably 70% by mass to 90% by mass, and even more preferably 80% by mass to 85% by mass.

[0026] The weight-average molecular weight (M) of the polyketone according to this embodiment. w The weight-average molecular weight (M) of the polyketone is not particularly limited, but is preferably 1,000 or more and 300,000 or less. w The reaction can be adjusted by the reaction solvent, reaction temperature, reaction time, monomer concentration, etc.

[0027] The number-average molecular weight (M) of the polyketone according to this embodiment. n The number average molecular weight (M) of the polyketone is not particularly limited, but is preferably 1,000 or more and 100,000 or less. n The reaction can be adjusted by the reaction solvent, reaction temperature, reaction time, monomer concentration, etc.

[0028] The polydispersity of polyketones according to this embodiment (M w / M n ) is not particularly limited, but is preferably 1 or more and 20 or less. The polydispersity (M w / M n ) can be adjusted by the reaction solvent, reaction temperature, reaction time, etc.

[0029] The number average molecular weight (M n ) and the weight average molecular weight (M w ) of the polyketone are measured by gel permeation chromatography graphy (GPC). The GPC analysis is performed under the following analysis conditions. Standard polystyrene is used for the preparation of the calibration curve. <GPC analysis conditions> Apparatus: HLC-8320 (manufactured by Tosoh Corporation) Column: TSKgel SuperHM-H × 2 columns (manufactured by Tosoh Corporation) Eluent: PFP / chloroform = 1 / 2 (wt / wt) Flow rate: 0.6 mL / min. <\(0000216\)> Temperature: 40 °C Sample concentration: 0.1% Injection volume: 20 μL Molecular weight standard: Polystyrene (manufactured by Tosoh Corporation)

[0030] 2. Method for producing polyketone The method for producing polyketone according to the present embodiment is not particularly limited, and may be a production method including any polymerization reaction using the monomers from which the above-described structural units are derived. As a production method including any polymerization reaction, a method including a reaction step of performing a Friedel-Crafts reaction is preferably mentioned. Hereinafter, a method for producing polyketone using a Friedel-Crafts reaction will be described.

[0031] 2-1. Reaction step 2-1-1. Monomer A method for producing polyketones using the Friedel-Crafts reaction preferably includes a reaction step in which an acid halide and an aromatic compound are reacted in the presence of a Lewis acid. Here, the acid halide includes an acid halide represented by formula (a1). The aromatic hydrocarbon includes an aromatic compound represented by formula (a2). The reaction between the acid halide represented by formula (a1) and the aromatic compound represented by formula (a2) forms a constituent unit represented by formula (A).

[0032] [ka]

[0033] p, q, and R 1 These are p, q, and R in equation (A), respectively. 1 It expresses the same meaning.

[0034] X represents a halogen group. Multiple Xs may be the same or different from one another, but it is preferable that they be the same.

[0035] Examples of halogen groups represented by X include chloro groups, bromo groups, and iodine groups, with chloro groups being preferred.

[0036] The following compounds are preferred as acid halides represented by formula (a1):

[0037] [ka]

[0038] Examples of aromatic compounds represented by formula (a2) include benzene, anisole, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, triphenylene, perylene, diphenyl ether, and diphenoxybenzene (preferably 1,4-diphenoxybenzene). Of these, the aromatic compound represented by formula (a2) is more preferably benzene, anisole, naphthalene, diphenyl ether, or diphenoxybenzene.

[0039] The acid halide represented by formula (a1) and the aromatic compound represented by formula (a2) can be produced by any method, including known methods and methods similar to known methods.

[0040] The content of the acid halide represented by formula (a1) in the total amount of acid halide is not particularly limited, but in order to fully exhibit the properties derived from the oligofuran skeleton, it is preferably 20 mol% to 100 mol%, more preferably 50 mol% to 95 mol%, even more preferably 70 mol% to 90 mol%, and even more preferably 80 mol% to 85 mol%.

[0041] The content of the aromatic compound represented by formula (a2) in the total amount of aromatic compounds is not particularly limited, but is preferably 20 mol% to 100 mol%, more preferably 50 mol% to 95 mol%, even more preferably 70 mol% to 90 mol%, and even more preferably 80 mol% to 85 mol%.

[0042] The amounts of acid halides and aromatic compounds used in the reaction process are not particularly limited, but the amount of aromatic compounds used is preferably 0.8 equivalents or more and 1.2 equivalents or less, more preferably 0.9 equivalents or more and 1.1 equivalents or less, and even more preferably 1.0 equivalent, relative to the amount of acid halides.

[0043] 2-1-2. Lewis Acids The reaction step is preferably carried out in the presence of a Lewis acid to promote the Friedel-Crafts reaction between the acid halide and the aromatic compound. The Lewis acid is not particularly limited as long as it catalyzes the Friedel-Crafts reaction, and examples include aluminum chloride (AlCl3), aluminum bromide (AlBr3), boron trifluoride (BF3), boron chloride (BCl3), iron chloride (FeCl3), and antimonyx fluoride. Examples of Lewis acids include ammonium compounds (SbF5), antimony chloride (SbCl5), indium chloride (InCl3), gallium chloride (GaCl3), zinc chloride (ZnCl2), zinc iodide (ZnI2), tin chloride (SnCl4), titanium chloride (TiCl4), and molybdenum chloride (MoCl5). Of these, aluminum chloride (AlCl3) is preferred as the Lewis acid because it can efficiently promote the reaction.

[0044] Lewis acids may be used individually, or two or more may be used in any combination and ratio.

[0045] The amount of Lewis acid used (amount charged) is not particularly limited, but is preferably 2 equivalents or more and 10 equivalents or less, more preferably 2 equivalents or more and 8 equivalents or less, and even more preferably 4 equivalents or more and 6 equivalents or less, relative to the amount of acid halide.

[0046] 2-1-3. Reaction solvent The reaction between acid halides and aromatic hydrocarbons is usually carried out in a solvent. The type of reaction solvent is not particularly limited as long as it can be used as a solvent for the Friedel-Crafts reaction, and can be appropriately selected depending on the solubility of the acid halide, aromatic compound, and the resulting polyketone.

[0047] Suitable reaction solvents include aprotic solvents (excluding those that are monomeric aromatic compounds). Preferred aprotic solvents include halogenated hydrocarbons such as dichloromethane and dichloroethane.

[0048] The reaction solvent may be used alone, or two or more solvents may be used in any combination and ratio.

[0049] 2-1-4. Additives The Friedel-Crafts reaction between an acid halide and an aromatic compound may be carried out in the presence of an additive if necessary. As the additive, known additives for the Friedel-Crafts reaction or similar additives can be used. Examples of known additives include those that form complexes with Lewis acids and act catalytically, such as N,N-dimethylformamide (DMF) and N-methylpyrrolidone (NMP). The additives may be used individually, or two or more may be used in any combination and ratio.

[0050] 2-1-5. Reaction Conditions The reaction conditions, such as reaction temperature and reaction time, should be appropriately set from among the reaction conditions commonly used in Friedel-Crafts reactions and polymer synthesis, depending on various factors such as the reactivity of the acid halide, the reactivity of the aromatic hydrocarbon, the stability of the polyketone, and the reaction scale. Suitable reaction conditions for the reaction process include the following:

[0051] (Atmospheric gas) The reaction process may be carried out under an inert atmosphere or under an atmospheric atmosphere, but it is preferable to carry it out under an inert atmosphere. Examples of inert atmospheres include nitrogen and argon. These inert gases may be used individually or two or more may be used in any combination and ratio. Furthermore, the reaction process may be carried out under atmospheric pressure or under pressurized conditions, but it is preferable to carry it out under atmospheric pressure.

[0052] (Reaction temperature) The reaction temperature is preferably 0°C to 120°C, more preferably 10°C to 100°C, even more preferably 20°C to 90°C, and even more preferably room temperature. In this disclosure, "room temperature" means a temperature condition in which no intentional heating or cooling is performed, and specifically means a temperature range of 20°C to 30°C. In this embodiment, the reaction between the acid halide and the aromatic hydrocarbon, particularly the acid halide represented by formula (a1) and the aromatic hydrocarbon represented by formula (a2), proceeds sufficiently even at room temperature, and can therefore be carried out under mild conditions. Furthermore, under room temperature conditions, the polyketone is less likely to decompose or depolymerize in the reaction solution, allowing for the acquisition of polyketone in good yield.

[0053] (Reaction time) The reaction time is preferably 30 minutes to 72 hours, more preferably 1 hour to 48 hours, and even more preferably 6 hours to 24 hours. By setting the reaction time within the above range, the reaction between the acid halide and the aromatic hydrocarbon can proceed sufficiently, and the decomposition of the resulting polyketone can be suppressed.

[0054] 2-2. Other processes In the production of polyketone according to this embodiment, other steps besides the reaction step may be performed. Other steps include, for example, a purification step in which the polyketone in the reaction solution is separated and purified after the reaction step. The separation and purification of the polyketone can be carried out by any method used in the field of polymer synthesis. Examples of any separation and purification method include filtration, adsorption, and reprecipitation.

[0055] 3. Uses of Polyketones The polyketone according to this embodiment exhibits excellent properties such as heat resistance, moldability, hardness, adhesion, and UV absorption, as shown in the examples described later. Therefore, the polyketone according to this embodiment is expected to be applicable to various applications where the above properties are required. For example, the polyketone according to this embodiment can be applied to plastic molded products such as sliding members, pipes, composites (e.g., polymer alloy members such as polymer blend members, and fiber-reinforced plastic members), resin laminates, powder coatings, films, and medical parts (e.g., implants). Furthermore, compositions containing polyketone, along with other components such as resins and additives as needed, can be applied to materials for the above-mentioned molded products and resin materials for 3D printing, and can therefore be used as resin compositions for plastic molded products and resin compositions for 3D printing.

[0056] The composition, which includes the polyketone according to this embodiment, along with a solvent and additives as needed, can be applied to applications such as adhesives, sealants, paints, and inks. Conventional polyketones have poor solubility and are unsuitable for these applications where dissolution in a solvent is required. However, the polyketone according to this embodiment exhibits good solubility in some solvents and can therefore be suitably used in such applications.

[0057] The polyketone according to this embodiment exhibits pH chromism, as shown in the examples described later. Therefore, the polyketone according to this embodiment can also be used as a pH indicator. [Examples]

[0058] The present disclosure will be further explained below with reference to examples, but these examples may be modified as appropriate without departing from the spirit of the present disclosure. Therefore, the scope of this disclosure should not be interpreted as being limited by the specific examples shown below.

[0059] <Instrumental analysis> <Nuclear magnetic resonance method ( 1 (H NMR)> Equipment: JNM-ECS400 NMR spectrometer (manufactured by JEOL Ltd.) Solvent: Deuterated chloroform Internal standard: Tetramethylsilane

[0060] <Infrared absorption spectroscopy (IR)> Equipment: FT / IR-4700 Fourier Transform Infrared Spectrophotometer (manufactured by JASCO Corporation) Measurement method: Single reflection total reflection attenuation (ATR) method Accessories: ATR PRO ONE (manufactured by JASCO Corporation), diamond prism

[0061] <Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF MS)> AXIMA Performance (Shimadzu Corporation) was used. Measurements were performed in Linear-positive ion mode. Dislanol was used as the matrix, and sodium trifluoroacetate or silver trifluoroacetate was used as the cationizing agent. THF solutions of each compound (matrix: 10 mg / mL, cationizing agent: 1.0 mg / mL, measurement sample: 1.0 mg / mL) were mixed in a matrix solution / cationizing agent solution / sample solution ratio of 10 / 1 / 1 to prepare the measurement sample. The measurement sample (10 μL) was placed on a sample target plate, dried under reduced pressure, and then measured.

[0062] <Differential thermogravimetry (TG / DTA) measurement> Equipment: Thermogravimetric and calorific simultaneous measurement device STA-6000 (manufactured by PerkinElmer) Sample bread: Ceramic bread Atmosphere: Nitrogen atmosphere (20 mL / min) Heating rate: 10.0℃ / min Measurement temperature range: 30℃~1,000℃

[0063] <Dynamic Viscoelasticity Measurement (DMA)> A DMA-8000 (Perkin Elmer) was used. A stainless steel material pocket was used to hold a solid sample, and measurements were performed in single cantilever mode under the following conditions: vibration frequency of 1.0 Hz, strain of 0.05 mm, and heating from 30°C to 250°C at a rate of 2°C / min.

[0064] <Measurement of UV and fluorescence properties> ·Ultraviolet / visible spectrometry (solution) Equipment: UV-Vis spectrophotometer UV, U-3000 (manufactured by Hitachi High-Tech Corporation) Samples were prepared by dissolving polyketones in a solvent and removing the solid from the resulting solution using a membrane filter. Ultraviolet-visible spectroscopy measurements of the polyketones were then performed using these samples. ·Ultraviolet / visible spectrometry (solid) Equipment: Ultraviolet-Visible-Near Infrared Spectrophotometer UH4150 (manufactured by Hitachi High-Tech Corporation) Solid samples of polyketones were placed directly into a cell, and ultraviolet-visible spectroscopy measurements of the polyketones were performed. • Spectrofluorescence measurement (solution) Equipment: Spectrofluorometer F-4500 (manufactured by Hitachi High-Tech Corporation) A sample was prepared by dissolving a polyketone in chloroform and removing the solid from the resulting solution using a membrane filter. Spectrofluorescence measurements of the polyketone were then performed using this sample. • Spectrofluorescence measurement (solid-state) Equipment: Spectrofluorometer F-4500 (manufactured by Hitachi High-Tech Corporation) Solid polyketone samples were placed directly into a cell, and spectroscopic fluorescence measurements of the polyketones were performed. . • Quantum yield Equipment: Absolute PL quantum yield analyzer C9920-02 (manufactured by Hamamatsu Photonics K.K.)

[0065] <Synthesis Example 1: Synthesis of Bifrancicarboxylic Acid Chloride> In a nitrogen-purged two-necked flask (20 mL), bifranjic acid (1.0 g, 4.5 mmol), thionyl chloride (5 mL, 139 mmol), and DMF (24 μL) were added and refluxed at 86 °C for 24 hours. The reaction mixture was slowly added to hexane (60 mL) and stirred for 30 minutes. The resulting precipitate was collected by suction filtration to obtain yellow crystals. These yellow crystals were purified by sublimation to obtain bifranjic acid chloride as a yellow solid (0.61 g, yield 54%).

[0066] 1 H NMR (400 MHz, Trifluoroacetic acid / CDCl3, 293 K): δ 7.59 (d, J = 4.0 Hz, 2H), 7.08 (d, J = 4.0 Hz, 2H) ppm.

[0067] <Example 1: Production of a polyketone (PBFK1) having an oligofuran skeleton> [ka]

[0068] In a nitrogen-purged two-necked flask (20 mL), bifrancicarboxylic acid chloride (0.21 g, 0.81 mmol), diphenyl ether (0.14 g, 0.81 mmol), dichloroethane (3.5 mL), and aluminum chloride (0.45 g, 3.4 mmol) were added and the mixture was stirred at -10°C for 1 hour. The reaction was then carried out at room temperature for 20 hours. Washing with methanol using Soxhlet extraction was performed for 24 hours, and the resulting solid was vacuum-dried to obtain PBFK1 as a yellowish-green solid (0.16 g, yield 56%).

[0069] <Example 2: Production of a polyketone (PBFK2) having an oligofuran skeleton> [ka]

[0070] In a nitrogen-purged two-necked flask (20 mL), bifrancicarboxylic acid chloride (0.21 g, 0.81 mmol), anisole (0.087 g, 0.81 mmol), dichloroethane (3.5 mL), and aluminum chloride (0.45 g, 3.4 mmol) were added and the mixture was stirred at -10°C for 1 hour. The reaction was then carried out at room temperature for 20 hours. Washing with methanol using Soxhlet extraction was performed for 24 hours, and the resulting solid was vacuum-dried to obtain PBFK2 as a yellow solid (0.19 g, yield 83%).

[0071] <Example 3: Production of a polyketone (PBFK3) having an oligofuran skeleton> [ka]

[0072] In a nitrogen-purged two-necked flask (20 mL), bifrancicarboxylic acid chloride (0.21 g, 0.81 mmol), benzene (0.06 g, 0.81 mmol), dichloroethane (3.5 mL), and aluminum chloride (0.45 g, 3.4 mmol) were added and the mixture was stirred at -10°C for 1 hour. The reaction was then carried out at room temperature for 20 hours. PBFK3 was obtained as a yellow solid (0.076 g, yield 36%) by washing with methanol using Soxhlet extraction for 24 hours and then vacuum drying the resulting solid.

[0073] <Example 4: Production of a polyketone (PBFK4) having an oligofuran skeleton> [ka]

[0074] In a nitrogen-purged two-necked flask (20 mL), bifrancicarboxylic acid chloride (0.21 g, 0.81 mmol), naphthalene (0.10 g, 0.81 mmol), dichloroethane (3.5 mL), and aluminum chloride (0.45 g, 3.4 mmol) were added and the mixture was stirred at -10°C for 1 hour. The reaction was then carried out at room temperature for 20 hours. Washing with methanol using Soxhlet extraction was performed for 24 hours, and the resulting solid was vacuum-dried to obtain PBFK4 as a yellow solid (0.106 g, yield 42%).

[0075] The polyketones obtained in Examples 1-4 1 Figure 1 shows the 1H NMR spectra, Figure 2 shows the IR spectra of the polyketones obtained in Examples 1-4, and Figure 3 shows the MALDI-TOF MS spectrum of the polyketone obtained in Example 1.

[0076] In the MALDI-TOF MS spectra of the polyketones obtained in Examples 1-4, repeating units formed by the reaction between bifrangic acid chloride and diphenyl ether were observed. Furthermore, the MALDI-TOF MS spectra indicate that the polyketones obtained in Examples 1 and 2 have more repeating units and a higher degree of polymerization than the polyketones obtained in Examples 3 and 4.

[0077] <Comparative Example 1: Production of polyketones (PPhK) without an oligofuran skeleton> [ka]

[0078] In a nitrogen-purged two-necked flask (20 mL), terephthalic acid dichloride (0.26 g, 1.27 mmol), diphenyl ether (0.20 mL, 1.27 mmol), dichloroethane (5.5 mL), and aluminum chloride (0.78 g, 5.33 mmol) were added and the mixture was stirred at -10°C for 1 hour. The reaction was then carried out at 45°C for 20 hours. PPhK was obtained by washing with methanol using Soxhlet extraction for 24 hours and then vacuum drying the resulting solid.

[0079] <Comparative Example 2: Production of Polyketones (PFK) Without an Oligofuran Skeleton> [ka]

[0080] In a nitrogen-purged two-necked flask (20 mL), francyl carboxylic acid dichloride (0.15 g, 0.81 mmol), diphenyl ether (0.14 g, 0.81 mmol), dichloroethane (3.5 mL), and aluminum chloride (0.45 g, 3.4 mmol) were added and the mixture was stirred at -10°C for 1 hour. The reaction was then carried out at room temperature for 20 hours. The solid was washed by Soxhlet extraction with methanol for 24 hours, and the resulting solid was vacuum-dried to obtain PFK as a white solid (0.129 g, yield 55%).

[0081] The polyketone obtained in Comparative Example 2 1 Figure 1 shows the 1H NMR spectra, and Figure 2 shows the IR spectra of the polyketones obtained in Comparative Examples 1 and 2.

[0082] <Confirmation of synthesis> The polyketones obtained in Examples 1-4 and Comparative Example 2 1 1H NMR spectra (Figure 1), IR spectra of polyketones obtained in Examples 1-4 and Comparative Examples 1-2 (Figure 2) at 1,700-1,800 cm⁻¹ -1 The observation of absorption of carbonyl bonds derived from the ketone, as well as the repeating peaks for the units in the MALDI-TOF-MS spectrum (Figure 3) of the polyketone obtained in Example 1, confirmed that the target polyketone had been synthesized.

[0083] <Evaluation of thermal properties> The thermal properties of polyketones were evaluated by TG / DTA and DMA measurements. The TGA curves for the polyketones obtained in Examples 1-4 and Comparative Examples 1-2 are shown in Figure 4, the DMA curves in Figure 5, and the 5% weight loss temperature, α relaxation temperature, and β relaxation temperature in Table 1.

[0084] [Table 1]

[0085] The 5% weight loss temperatures of the polyketones obtained in Examples 1-4 were slightly lower than those of the polyketone obtained in Comparative Example 1, but were above 300°C except for Example 2. Therefore, it can be seen that polyketones having an oligofuran skeleton have high heat resistance.

[0086] <Evaluation of solubility and solution color> The polyketone obtained in Example 1 (5 mg) and the polyketone obtained in Comparative Example 1 (5 mg) were each mixed with 5 mL of solvent, and the solubility and solution strength of the resulting test solutions were evaluated by visual observation. The results are shown in Table 2.

[0087] [Table 2]

[0088] As can be seen from Table 2, the polyketone obtained in Comparative Example 1 was soluble in sulfuric acid, but only partially soluble in hexafluoroisopropanol and trifluoroacetic acid. On the other hand, the polyketones obtained in Examples 1 to 4 were soluble in trifluoroacetic acid and sulfuric acid, and also partially soluble in hexafluoroisopropanol and formic acid. These results indicate that polyketones with an oligofuran skeleton have higher solubility in acids than polyketones without an oligofuran skeleton.

[0089] As can be seen from Table 2, the color of the polyketone solutions obtained in Comparative Examples 1 and 2 was independent of the solvent type and remained almost unchanged even when the type of solvent was changed. On the other hand, the polyketone solutions obtained in Examples 1 to 4 exhibited different colors depending on the solvent type. From this, it was inferred that the polyketones obtained in Examples 1 to 4 exhibit solvatochromism due to the presence of an oligofuran skeleton. Therefore, the solvatochromism of polyketones with an oligofuran skeleton was investigated below.

[0090] <Investigation of Solvatochromism> Samples were prepared by dissolving the polyketone obtained in Example 1 in trifluoroacetic acid, hexafluoroisopropanol, and formic acid, respectively, and ultraviolet-visible spectroscopy measurements were performed. The obtained ultraviolet-visible absorption and fluorescence spectra are shown in Figure 6. The maximum absorption wavelength, fluorescence emission wavelength, quantum yield, and Stokes shift of the polyketone obtained in Example 1 are shown in Table 3.

[0091] [Table 3]

[0092] The polyketone solutions obtained in Example 1 exhibited different absorption and fluorescence wavelengths depending on the solvent used. This indicates that polyketones with an oligofuran skeleton exhibit solvatochromism.

[0093] <Evaluation of Spectroscopic Properties> The spectroscopic properties of polyketones were evaluated by ultraviolet-visible spectroscopy and spectrofluorescence measurements. The ultraviolet-visible absorption spectra and fluorescence spectra of the polyketones obtained in Examples 1-4 and Comparative Example 2 are shown in Figure 7, and the spectroscopic parameters are shown in Table 4.

[0094] [Table 4]

[0095] The polyketone obtained in Example 1 had a maximum absorption wavelength of 400 nm and a maximum fluorescence wavelength of 519 nm. These results indicate that polyketones with an oligofuran skeleton exhibit UV absorption and fluorescence emission due to the oligofuran skeleton.

[0096] <Investigation of UV-Vis absorption and fluorescence emission in the solid state> Figure 8 shows the ultraviolet-visible absorption spectra and fluorescence spectra of the polyketones obtained in Examples 1-4 and Comparative Examples 1-2 in the solid state. Table 5 shows the maximum absorption wavelength, fluorescence emission wavelength, quantum yield, and Stokes shift of the polyketones obtained in Examples 1-4 and Comparative Examples 1-2.

[0097]

Table 5

[0098] In the ultraviolet-visible spectroscopic measurements of the polyketones obtained in Examples 1 to 4, strong fluorescence emission was observed. On the other hand, in the ultraviolet-visible spectroscopic measurements of the polyketone obtained in Comparative Example 1, no fluorescence emission was observed. From these facts, it can be said that the fluorescence emission exhibited by the polyketones obtained in Examples 1 to 4 is due to the oligofuran skeleton to which the furan ring is linked. In addition, since the polyketone obtained in Example 1 has a larger Stokes shift and a larger quantum yield than the polyketone obtained in Comparative Example 2, it can be seen that the bifuran skeleton can endow the polyketone with better fluorescence properties than the monofuran skeleton.

[0099] <Examination of pH chromism> The polyketone (10 mg, 0.027 mmol) obtained in Example 1 was dissolved in 3 mL of trifluoroacetic acid to prepare a polyketone solution of 3.3 mg / mL. This polyketone solution was dropped onto a glass substrate to prepare a solid film A. The solid film A was subjected to a base treatment by dropping a 5% aqueous sodium hydroxide solution onto the solid film A to obtain a solid film B. Further, the solid film B was subjected to an acid treatment by dropping 1 M hydrochloric acid onto the solid film B to obtain a solid film C.

[0100] The ultraviolet-visible absorption spectra and fluorescence spectra of the solid films A to C are shown in FIG. 9. In addition, Table 6 shows the maximum absorption wavelength, fluorescence emission wavelength, quantum yield, and Stokes shift of the polyketone constituting the solid films A to C.

[0101]

Table 6

[0102] Since the ultraviolet-visible absorption spectrum and fluorescence spectrum of the polyketone obtained in Example 1 change according to the change in pH, it can be seen that it exhibits pH chromism.

[0103] <Evaluation of coating film> (Preparation of coating film) The polyketones obtained in Example 1 and Comparative Example 2 (10 mg and 0.027 mmol) were dissolved in 3 mL of trifluoroacetic acid, respectively, to prepare a 3.3 mg / mL polyketone solution. The polyketone solution was dropped onto polyethylene terephthalate (PET) plates, glass plates, and stainless steel plates, respectively, and dried to produce a coating film (cast film).

[0104] (Evaluation of coating hardness) Scratch hardness tests were conducted in accordance with JIS K 5600-5-4:1999 ("General test methods for paints - Part 5: Mechanical properties of paint films - Section 4: Scratch hardness (pencil method)", published May 31, 1999).

[0105] The pencil was sharpened with a cutter, exposing approximately 5 mm of lead, and the tip was flattened with sandpaper. The pencil lead was flattened with sandpaper each time before use. Marks were made on the coating at 7 mm intervals with a pen. The pencil was placed in a scratch hardness test device, and while measuring with a timer, the device was pressed at 1 mm / s, and lines were drawn with the pencil. The coating was traced with a plastic spatula and visually inspected for scratches. The test was repeated, starting with a 6B pencil and increasing the hardness until scratches of 3 mm or more appeared on the coating. Three tests were performed on each type of coating, and the mode was adopted as the pencil hardness of the coating. The results are shown in Table 7.

[0106] [Table 7]

[0107] The polyketone coatings obtained in Example 1, formed on PET plates, glass plates, and stainless steel plates, exhibited high hardness. Similarly, the polyketone coatings obtained in Examples 2-4, formed on PET plates, also exhibited high hardness. These results demonstrate that polyketones with an oligofuran skeleton can form hard coatings on various substrates such as resins, metals, and glass.

[0108] (Evaluation of coating adhesion) The adhesion of the coating film was evaluated using the cross-cut method in accordance with JIS K 5600-5-6:1999 ("General test methods for coatings - Part 5: Mechanical properties of coating films - Section 6: Adhesion (cross-cut method)", published May 31, 1999).

[0109] Six cuts were made in the coating film at 1 mm intervals using a cutter. Then, six more cuts were made perpendicular to the first cut at 1 mm intervals, with the direction changed by 90°. A cellophane tape approximately 75 mm long was attached to the coating film, and the tape was peeled off after 0.5 to 1.0 seconds. The condition of the coating film was evaluated according to classification 0 to 5 as described in JIS K 5600-5-6:1999. The results are shown in Table 8.

[0110] [Table 8]

[0111] The polyketone coating obtained in Example 1 exhibited particularly excellent adhesion to PET plates and stainless steel plates, and was confirmed to adhere well to glass plates as well. These results indicate that polyketones with an oligofuran skeleton exhibit high adhesion to substrates of various materials such as resins, metals, and glass.

Claims

1. A polyketone having a constituent unit represented by formula (A). 【Chemistry 1】 (In the formula, p represents an integer between 2 and 8; R １ R represents an aromatic hydrocarbon group having 6 to 24 carbon atoms, which may have substituents, or an aromatic heterocyclic group having 4 to 24 carbon atoms, which may have substituents; multiple R １ (These can be the same or different from each other; q represents an integer between 0 and 3, inclusive.)

2. The aforementioned R １ The polyketone according to claim 1, wherein the aromatic hydrocarbon group having 6 to 24 carbon atoms may have substituents, and q is 0 or 1.

3. The polyketone according to claim 1, wherein p is 2 or 4.

4. A plastic molded article comprising the polyketone described in any one of claims 1 to 3.

5. A plastic molded article according to claim 4, which is a sliding member, pipe, composite, resin laminate, powder coating, film, or medical part.

6. A polyketone composition comprising the polyketone described in any one of claims 1 to 3.

7. The polyketone composition according to claim 6, which is a resin composition for 3D printing.

8. The polyketone composition according to claim 6, further comprising a solvent, wherein the polyketone is dissolved in the solvent.

9. The polyketone composition according to claim 8, used in paints, adhesives, sealants, or inks.

10. A pH indicator comprising a polyketone according to any one of claims 1 to 3.

11. A method for producing a polyketone, comprising a reaction step of reacting an acid halide with an aromatic hydrocarbon in the presence of a Lewis acid, The acid halide includes an acid halide represented by formula (a1), A method for producing a polyketone, wherein the aromatic hydrocarbon includes an aromatic compound represented by formula (a2). 【Chemistry 2】 (In the formula, p represents an integer between 2 and 8; X represents a halogen group; multiple Xs may be the same or different from each other; R １ R represents an aromatic hydrocarbon group having 6 to 24 carbon atoms, which may have substituents, or an aromatic heterocyclic group having 4 to 24 carbon atoms, which may have substituents; multiple R １ (These can be the same or different from each other; q represents an integer between 0 and 3, inclusive.)

12. The aforementioned R １ The method for producing a polyketone according to claim 11, wherein the aromatic hydrocarbon group having 6 to 24 carbon atoms may have substituents, and q is 0 or 1.

13. The method for producing a polyketone according to claim 11 or 12, wherein p is 2 or 4.

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