Polyether nitriles and polyether nitrile particles

Abstract

A polyether nitrile represented by formula (I) in which, in a proton NMR measurement using a mixed solvent in which the volume ratio of pentafluorophenol to deuterated chloroform is 5: 4, "the integrated value of peak A (peak having a peak top at 7.10-7.20 ppm) / the integrated value of peak B (peak having a peak top at 7.55-7.68 ppm)" is 0.050 or less. Provided is a polyether nitrile having high thermal stability.

Description

Technical Field

[0001] This invention relates to polyether nitrile and polyether nitrile particles. Background Technology

[0002] Polyether nitrile is a high-performance super engineering plastic with excellent thermal stability, chemical resistance, flame retardancy, as well as excellent mechanical properties such as wear resistance and friction resistance.

[0003] Although polyether nitrile has the high performance mentioned above, higher thermal stability is required due to the increasing demands on the properties of raw materials in recent years.

[0004] Furthermore, the active functional group ends present in polymers are generally envisioned as functioning as reaction sites for polymer reactions and interaction sites with additives; however, on the other hand, they can also contribute to decreased thermal stability. Patent Document 1 discloses a method for using monosubstituted halogen compounds to control molecular weight during the polymerization of polyether nitrile.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 63-270733 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] However, the improvement in the thermal stability of polyether nitrile described in Patent Document 1 is insufficient. Furthermore, Patent Document 1 does not describe the mechanisms or factors that enable control of the end structure and thermal stability. Additionally, the method shown in Patent Document 1 requires the use of a third component other than the monomer to seal the polymer ends, leaving room for improvement in terms of processability and economy.

[0010] Therefore, in view of the problems of these prior art, the inventors have taken the provision of polyether nitrile with excellent thermal stability as their objective.

[0011] Methods for solving problems

[0012] The inventors of this invention conducted in-depth research to solve the aforementioned problems and discovered an analytical method that has long been difficult to implement for analyzing and quantifying the end structure of polyether nitrile. Furthermore, based on this analytical method, they analyzed the relationship between the end structure and thermal stability of polyether nitrile and discovered a method for controlling the end structure. Moreover, they found that polyether nitrile meeting specific conditions exhibits excellent thermal stability, thus completing this invention. In other words, this invention has the following structure.

[0013] (1) A polyether nitrile, as shown in formula (I), wherein in proton NMR determination using a mixed solvent of pentafluorophenol and deuterated chloroform at a volume ratio of 5:4, the integral value of peak A / integral value of peak B is less than 0.050.

[0014] Peak A: A peak with a apex in the range of 7.10–7.20 ppm.

[0015] Peak B: A peak with a apex in the range of 7.55–7.68 ppm.

[0016]

[0017] In equation (I), Ar is a unit represented by any of the equations (a) to (f), and Ar can be composed of one or more types of units.

[0018]

[0019] (2) According to the polyether nitrile described in (1), in the proton NMR determination using a mixed solvent of pentafluorophenol and deuterated chloroform in a volume ratio of 5:4, the "integral value of the peak at the end / integral value of peak B" is 0.001 to 0.055.

[0020] (3) The polyether nitrile according to (1) or (2), wherein Ar is composed of two or more units.

[0021] (4) A polyether nitrile particle formed from any one of (1) to (3), wherein the number-average particle size of the polyether nitrile particle is 0.1 to 200 μm.

[0022] (5) A component for a moving body, comprising any one of (1) to (3) a polyether nitrile.

[0023] (6) A structural material component comprising any one of (1) to (3) a polyether nitrile.

[0024] (7) An electrical / electronic material component comprising any one of (1) to (3) polyether nitrile.

[0025] (8) A mobile body that uses the mobile body component described in (5).

[0026] (9) A structural material that uses the structural material components described in (6).

[0027] (10) An electrical / electronic product that uses components made of the electrical / electronic material described in (7).

[0028] The effects of the invention

[0029] According to the present invention, polyether nitrile with excellent thermal stability can be provided. Detailed Implementation

[0030] The present invention will now be described in detail along with its embodiments.

[0031] (1) Polyether nitrile

[0032] The polyether nitrile of the present invention is the polyether nitrile shown in formula (I).

[0033]

[0034] In equation (I), Ar is a unit represented by any of the units in equations (a) to (f). Ar can be composed of one or more units.

[0035]

[0036] In the polyether nitrile of the present invention, Ar can be composed of two or more units.

[0037] When Ar is composed of two types of units, and the polyether nitrile contains N repeating units of the first type represented by Ar and M repeating units of the second type represented by Ar, the content (molar ratio) of the repeating units of the first type represented by Ar relative to all Ar is represented by [N / (N+M)]. It should be noted that the relationship between N and M here is set to N≥M. In this case, if a polyether nitrile with a lower melting point is desired, it is preferable that [N / (N+M)] < 1.00. Furthermore, to obtain a polyether nitrile with high crystallinity, it is preferable that 0.8 ≤ [N / (N+M)]. A low melting point is preferred for obtaining polyether nitrile with excellent processability. On the other hand, high crystallinity is preferred for obtaining polyether nitrile with excellent mechanical properties.

[0038] In addition, the polyether nitrile in this invention can be end-modified using a capping agent.

[0039] When proton NMR was measured using a mixed solvent of pentafluorophenol and deuterated chloroform in a volume ratio of 5:4, the ratio of the integral value of peak A to the integral value of peak B, "integral value of peak A / integral value of peak B", of the polyether nitrile of the present invention was 0.050 or less.

[0040] Peak A: A peak with a apex in the range of 7.10–7.20 ppm.

[0041] Peak B: A peak with a apex in the range of 7.55–7.68 ppm.

[0042] The integral value of peak A / integral value of peak B is preferably 0.040 or less, more preferably 0.020 or less, and most preferably 0. It should be noted that the integral value of peak A / integral value of peak B is 0 or more.

[0043] Here, peak A is the peak with a apex in the 7.10–7.20 ppm range of proton NMR measurements. It should be noted that when multiple peaks exist in the 7.10–7.20 ppm range, the integrated value of peak A refers to the sum of the integrated values ​​of all these peaks within the 7.10–7.20 ppm range. Similarly, peak B is the peak with a apex in the 7.55–7.68 ppm range of proton NMR measurements. Again, it should be noted that when multiple peaks exist in the 7.55–7.68 ppm range, the integrated value of peak B refers to the sum of the integrated values ​​of all these peaks within the 7.55–7.68 ppm range.

[0044] In addition, when polymers and additives other than polyether nitrile are included, it is preferable to perform proton NMR determination in a state in which polymers and additives other than polyether nitrile are removed.

[0045] Peak A above represents the peak of the aromatic ring at the end of the polymer of polyether nitrile, specifically the peak of the proton adjacent to the active group of the aromatic ring having an active group that adversely affects thermal stability. When this active group is a hydroxyl group from a diol monomer, a peak with two protons appears in the region of peak A, relative to one hydroxyl terminus. Here, "hydroxyl terminus" refers to the hydroxyl group present in the aromatic ring at the end of the polymer.

[0046] Peak B above represents the peak of protons in the aromatic rings with nitrile groups contained in the repeating units of the polymer chain constituting the polyether nitrile. In the region of peak B, a peak of 1 proton appears relative to one aromatic ring with a nitrile group.

[0047] That is, "the integral value of peak A / the integral value of peak B" represents the proportion of active groups at the polymer ends of the polyether nitrile polymer chain that adversely affect thermal stability. Polar functional groups such as hydroxyl groups can be cited as examples of active groups that adversely affect thermal stability.

[0048] There are no particular limitations on the method used to make the integral value of peak A / integral value of peak B less than 0.050. For example, it can be achieved by either of the following two methods.

[0049] As method 1, in the method for manufacturing polyether nitrile described later, in the relationship between the aromatic compound with two hydroxyl groups substituted and the aromatic compound with a benzyl nitrile skeleton substituted with two halogen groups substituted, it is preferable that the proportion of the aromatic compound with a benzyl nitrile skeleton substituted with two halogen groups is in excess compared to the aromatic compound with two hydroxyl groups substituted. In this case, the polyether nitrile obtained after polymerization can have fewer hydroxyl terminals from the aromatic compound with two hydroxyl groups substituted, and the "integral value of peak A / integral value of peak B" can be 0.050 or less.

[0050] It should be noted that, in order to ensure that the ratio of the integral value of peak A to the integral value of peak B is below 0.050, it is preferable to allow sufficient reaction time in the polymerization reaction to complete the polymerization. To ensure polymerization completion, it is preferable to react for at least 6 hours after reaching the target maximum reaction temperature. To confirm the completion of polymerization, a sample of the reaction solution can be taken and proton NMR measured using a mixed solvent of pentafluorophenol and deuterated chloroform at a volume ratio of 5:4. The completion of polymerization can be confirmed by the invariance of the ratio of the end peak to the integral value of peak B in the proton NMR measurement.

[0051] When using NMP as the polymerization solvent and carrying out the polymerization reaction at 200°C, the reaction time at 200°C is preferably 6 to 10 hours, more preferably 8 to 10 hours, to ensure the polymerization is complete. By reacting at 200°C for 6 hours or more, the polymerization can be expected to be completed.

[0052] Alternatively, as method 2, the hydroxyl ends can be blocked by using end-capping agents, thereby reducing the number of hydroxyl ends and making the ratio of peak A's integral value to peak B's integral value less than 0.050. Examples of end-capping agents include compounds that react with phenolic hydroxyl groups, such as organohalides. By incorporating end-capping agents during the polymerization of polyether nitrile or when mixing polyether nitrile with other components, the ratio of peak A's integral value to peak B's integral value can be made less than 0.050.

[0053] From the perspective of not requiring components other than monomers, such as end-capping agents, method 1 is preferred. Alternatively, methods 1 and 2 can be used together.

[0054] In the proton NMR determination of the polyether nitrile of the present invention using a mixed solvent of pentafluorophenol and deuterated chloroform at a volume ratio of 5:4, the integral value of the terminal peak / integral value of peak B is preferably 0.001 to 0.055. The integral value of the terminal peak / integral value of peak B is an indicator of the polymer length of the polyether nitrile. The larger the integral value of the terminal peak / integral value of peak B, the shorter the polymer length of the polyether nitrile. For polyether nitrile with high mechanical properties, a small integral value of the terminal peak / integral value of peak B is preferred. For polyether nitrile with excellent processability and low viscosity, a large integral value of the terminal peak / integral value of peak B is preferred. Although the preferred range varies depending on the purpose, as a range that balances the mechanical properties and processability of the polyether nitrile, the integral value of the terminal peak / integral value of peak B is more preferably 0.010 to 0.050, and even more preferably 0.020 to 0.040.

[0055] It should be noted that, regarding the peaks representing the ends mentioned above, in the case of polyether nitrile monomers using only aromatic compounds substituted with two hydroxyl groups and aromatic compounds with a benzyl nitrile skeleton substituted with two halogen groups, the polymer's end structure is either a hydroxyl end or a halogen end. Regarding the hydroxyl end, as mentioned above, it is an aromatic ring with hydroxyl groups, represented by peak A, which apexes at 7.10–7.20 ppm in proton NMR measurements. On the other hand, the halogen end is an aromatic ring with halogen substituents. In proton NMR measurements, if the peak of the aromatic ring with halogen substituents is designated as peak C, then peak C is a peak apexizing at 6.95–7.00 ppm. A peak with one proton fraction appears in the peak C region relative to an aromatic ring with halogen substituents. Therefore, the aforementioned "integral value representing the end peak" is "the sum of the integral values ​​of peak A and peak C" (hereinafter, sometimes referred to as the integral value of peak (A+C)).

[0056] Furthermore, in cases where polyether nitriles are end-modified using a capping agent in addition to using aromatic compounds with two hydroxyl groups substituted for each hydroxyl group and aromatic compounds with a benzyl nitrile skeleton substituted for two halogen groups as monomers, the term "integral value representing the terminal peak" is "the sum of the integral values ​​of peak A, peak C, and the peak from the capping agent." Peak A represents the amount of hydroxyl terminals present, with a peak of 2 protons for each hydroxyl terminal. Peak C represents halogen terminals, with a peak for each halogen terminal. When a capping agent blocking the hydroxyl terminals is used, the number of protons from the peaks introduced into the terminals, regardless of the number of protons per structural unit (e.g., whether it is 1 proton or 4 protons), is summed based on a conversion to 2 protons. That is, for example, in proton NMR measurements, when the number of protons per structural unit of the peak from the capping agent is 4 protons, the integral value of the peak from the capping agent is divided by 2 to obtain an area value of 2 protons, which is then summed with the integral values ​​of peak A and peak C. Furthermore, when a capping agent blocking halogen ends is used, regardless of the number of protons per structural unit of the peak from the capping agent introduced to the end, it is converted to 1 proton and summed. That is, for example, in proton NMR measurements, when the number of protons in the peak from the capping agent is 3 protons, the integral value of the peak from the capping agent is divided by 3 to obtain an area value of 1 proton, which is then summed with the integral values ​​of peak A and peak C.

[0057] The melting point of the polyether nitrile of the present invention is preferably 280~360°C, more preferably 280~350°C, from the viewpoint of processability.

[0058] The terminal group of the polyether nitrile of the present invention is not limited, but is generally selected from hydroxyl groups, metal salts of hydroxyl groups, halogenated groups, linear organic groups with 1 to 16 carbon atoms, branched organic groups, and cyclic organic groups.

[0059] The polyether nitrile of the present invention exhibits excellent thermal stability by having an integral value of peak A / integral value of peak B of 0.050 or less in proton NMR measurements using a mixed solvent of pentafluorophenol and deuterated chloroform at a volume ratio of 5:4. In the present invention, "excellent thermal stability" refers to a low rate of weight loss when heated from 50°C to the melting point +30°C in air at a heating rate of 20°C / min and held at the melting point +30°C for 30 minutes in thermogravimetric analysis (TG), or a low rate of viscosity increase when held at the melting point +30°C in air for 30 minutes in rheometer measurements. More preferably, the polyether nitrile of the present invention exhibits a low rate of weight loss when heated from 50°C to the melting point +30°C in air at a heating rate of 20°C / min and held at the melting point +30°C for 30 minutes in thermogravimetric analysis (TG), and a low rate of viscosity increase when held at the melting point +30°C in air for 30 minutes in rheometer measurements.

[0060] The weight loss rate of the polyether nitrile of the present invention, when heated from 50°C to its melting point +30°C in air at a heating rate of 20°C / min and held at the melting point +30°C for 30 minutes in thermogravimetric analysis (TG), is preferably 0.8% or less, more preferably 0.6% or less, and even more preferably 0.4% or less. It should be noted that the weight loss rate is calculated based on the weight after holding at 50°C for 1 minute.

[0061] The viscosity increase rate of the polyether nitrile of the present invention, when measured in a rheometer at its melting point +30°C for 30 minutes in air, is preferably 70% or less, more preferably 60% or less, and even more preferably 35% or less. This viscosity increase is presumably due to oxidation in air. It is presumed that because polyether nitrile has active terminals such as hydroxyl groups, oxidation in air accelerates the viscosity increase.

[0062] The polyether nitrile of the present invention can be molded by methods such as injection molding, injection compression molding, blow molding, and extrusion molding. During molding, polyether nitrile can be used alone, or it can be used to form a composition, as desired, blended with inorganic fillers such as glass fiber, carbon fiber, titanium dioxide, and calcium carbonate, as well as additives such as antioxidants, heat stabilizers, ultraviolet absorbers, and colorants. Alternatively, resins other than the polyether nitrile of the present invention can also be blended during molding.

[0063] The polyether nitrile of the present invention exhibits excellent thermal stability, making it suitable for use in components for moving bodies, electrical / electronic materials, structural materials, household / office electrical products, optical equipment / precision machinery components, water-related components, and other industrial applications. Examples of moving body components include those for automobiles, aircraft, ships, motorcycles, drones, urban air transportation, and scooters. Examples of electrical / electronic material components include those for integrated circuits, connectors, and insulators. Examples of structural material components include those for buildings, bridges, railways, roads, and harbors. The polyether nitrile of the present invention is suitable for moving body components, electrical / electronic material components, or structural material components where particularly excellent thermal stability is required.

[0064] Mobile bodies using mobile body components incorporating the polyether nitrile of the present invention exhibit excellent properties. Examples of mobile bodies according to the present invention include automobiles, aircraft, ships, motorcycles, drones, urban air traffic, and scooters.

[0065] Electrical / electronic products using components made of the polyether nitrile electrical / electronic material of the present invention exhibit excellent properties. Examples of electrical / electronic products according to the present invention include integrated circuits, connectors, and insulators.

[0066] Structural materials using structural materials incorporating the polyether nitrile of the present invention exhibit excellent properties. Examples of structural materials according to the present invention include buildings, bridges, railways, roads, harbors, etc.

[0067] The polyether nitrile particles of the present invention are polyether nitrile particles formed from the polyether nitrile of the present invention, having a number average particle size of 0.1 μm or more and 200 μm or less. By having a number average particle size of 200 μm or less, the surface of coatings and the like made from the particles can be easily made homogeneous. In addition, by having a number average particle size of 0.1 μm or more, the aggregation of particles can be easily suppressed. If the number average particle size of the polyether nitrile particles is 100 μm or less, it is suitable for application in powder coating and the like, and is therefore preferred. By having a number average particle size of 100 μm or less, the surface of coatings and the like made from the particles becomes homogeneous.

[0068] As a method for obtaining polyether nitrile particles with a number-average particle size within the aforementioned range, methods that modify the particle formation conditions can be cited. For example, by changing the composition of the undesirable solvent described later, the number-average particle size can be controlled. Other methods include pulverizing the particles or polymer blocks, or dissolving them and then re-particle-forming them.

[0069] (2) Method for manufacturing polyether nitrile

[0070] The method for manufacturing the polyether nitrile of the present invention is not particularly limited as long as it can synthesize a polyether nitrile that satisfies the requirements of (1) above, and any method can be used. For example, the polyether nitrile of the present invention can be manufactured by heating an aromatic compound substituted with two hydroxyl groups, an aromatic compound having a benzyl nitrile skeleton substituted with two halogen groups, and a base in an organic polar solvent.

[0071] The following describes an example of the method for manufacturing the polyether nitrile of the present invention, which uses an aromatic compound substituted with two hydroxyl groups, an aromatic compound having a benzyl nitrile skeleton substituted with two halogen groups, a base, an organic polar solvent, and reaction conditions.

[0072] As an aromatic compound substituted with two hydroxyl groups and used as a monomer in the method of manufacturing the polyether nitrile of the present invention, examples of compounds shown in any of the following general formulas (g) to (l) can be cited.

[0073]

[0074] As an aromatic compound substituted with two hydroxyl groups, compounds selected from resorcinol, hydroquinone, 4,4'-dihydroxybiphenyl, 2,2'-bis(4-hydroxyphenyl)propane, and bis(4-hydroxyphenyl)sulfone are more preferred. Two or more compounds substituted with two hydroxyl groups may be used.

[0075] In the method of manufacturing the polyether nitrile of the present invention, the so-called compound having a benzyl nitrile skeleton substituted with two halogen groups can be a compound represented by the following formula (m).

[0076]

[0077] X is a chlorine atom or a fluorine atom. Examples of compounds having a benzyl nitrile skeleton that are substituted with two halogen groups include 2,6-dichlorobenzyl nitrile, 2,6-difluorobenzyl nitrile, and 2-chloro-6-fluorobenzyl nitrile, with 2,6-dichlorobenzyl nitrile being preferred.

[0078] The so-called base used in the method for manufacturing the polyether nitrile of the present invention can be an organic base or an inorganic base. Specifically, examples include organic bases such as 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene, and 1,5,7-triazabicyclo[4.4.0]deca-5-ene; carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate; carbonates of alkaline earth metals such as calcium carbonate, strontium carbonate, and barium carbonate; bicarbonates of alkali metals such as lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, and cesium bicarbonate; bicarbonates of alkaline earth metals such as calcium bicarbonate, strontium bicarbonate, and barium bicarbonate; or hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide; and hydroxides of alkaline earth metals such as calcium hydroxide, strontium hydroxide, and barium hydroxide. From the viewpoint of ease of handling / reactivity, carbonates such as sodium carbonate and potassium carbonate are preferred; and bicarbonates such as sodium bicarbonate and potassium bicarbonate are even more preferred, with sodium carbonate or potassium carbonate being the most preferred, and sodium carbonate being the most preferred. They can be used alone or in mixtures of two or more. Furthermore, these bases are preferably used in anhydrous form, but can also be used as hydrates or aqueous mixtures. It should be noted that the term "aqueous mixture" here refers to an aqueous solution, a mixture of an aqueous solution and a solid component, or a mixture of water and a solid component.

[0079] The amount of alkali used in the method for manufacturing the polyether nitrile of the present invention depends on the amount of the aromatic compound substituted with two hydroxyl groups. When using a monovalent alkali, at least 2 equivalents, preferably 2.2 equivalents or more, and more preferably 2.4 equivalents or more, are required relative to the aromatic compound substituted with two hydroxyl groups. Sufficient alkali mixing ensures that, in proton NMR measurements of the resulting polyether nitrile using a mixed solvent of pentafluorophenol and deuterated chloroform at a volume ratio of 5:4, the integral value of peak A / integral value of peak B can be small. Furthermore, when using a divalent alkali such as sodium carbonate, at least 1 equivalent, preferably 1.1 equivalents or more, and more preferably 1.2 equivalents or more, are required relative to the aromatic compound substituted with two hydroxyl groups. It should be noted that even with further excess alkali, production can proceed without problems; therefore, there is no particular upper limit, but in practice, it is 10 equivalents or less.

[0080] In the preferred method for manufacturing the polyether nitrile of the present invention, there are no particular limitations on the organic polar solvent used, as long as it does not hinder the reaction. Specific examples of such organic polar solvents include nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolium ketone (DMI), hexamethylphosphoramide, and tetramethylurea; sulfoxide / sulfone solvents such as dimethyl sulfoxide (DMSO), dimethyl sulfone, diphenyl sulfone, and sulfolane; nitrile solvents such as benzyl nitrile; diaryl ethers such as diphenyl ether; ketones such as benzophenone and acetophenone; and mixtures thereof. Since they all have high reaction stability, they are preferred to be used, but among them, solvents selected from NMP, DMSO, and sulfolane are preferred, and NMP is particularly preferred. From the viewpoint of excellent stability in the high-temperature region and thus ease of use, these organic polar solvents can also be considered preferred organic polar solvents.

[0081] During the manufacture of polyether nitrile, water is generated as a byproduct of the reaction. To remove this byproduct water, an organic compound that forms an azeotropic mixture with water can be added as needed. There are no particular restrictions on such organic compounds as long as they form an azeotropic mixture with water, but a nonpolar organic solvent with a boiling point lower than that of the reaction solvent is preferred; toluene is a specific example.

[0082] The method for manufacturing the polyether nitrile of the present invention is generally carried out under a nitrogen atmosphere or reduced pressure and under heating. The reaction temperature can vary over a wide range, but it is preferably carried out at a temperature of 80°C or higher, more preferably 150°C or higher. From a manufacturability point of view, it is preferable to carry out the reaction at a temperature of 400°C or lower, more preferably 350°C or lower. Considering the sublimation and reactivity of the compound used, it is preferable to carry out the reaction while gradually increasing the temperature in stages within the range of 150 to 350°C, more preferably within the range of 150 to 200°C.

[0083] By separating and recovering the reaction mixture obtained through the above-described operation, the polyether nitrile of the present invention can be obtained. The reaction mixture obtained by the above manufacturing method contains at least polyether nitrile, and may also contain oligomers, byproduct salts, unreacted bases, etc., as other components. There are no particular limitations on the method for recovering polyether nitrile from such a reaction mixture; examples include methods such as contacting it with a solvent soluble in the byproduct salts under heating as needed, or methods for removing the byproduct salts and oligomers under reduced pressure.

[0084] Solvents that are soluble in byproduct salts are generally preferred to be highly polar solvents. The preferred solvent varies depending on the type of alkali and byproduct salt used, and therefore cannot be limited. Examples include: water; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, and hexanol; ketones such as acetone and methyl ethyl ketone; acetates such as ethyl acetate and butyl acetate; nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolium ketone (DMI), hexamethylphosphoramide, and tetramethylurea; sulfoxide / sulfone solvents such as dimethyl sulfoxide (DMSO), dimethyl sulfone, diphenyl sulfone, and sulfolane; and acids such as acetic acid, hydrochloric acid, sulfuric acid, and nitric acid. From the viewpoints of accessibility and economy, solvents selected from water, methanol, acetone, acetic acid, hydrochloric acid, sulfuric acid, and NMP are preferred, with water, acetic acid, hydrochloric acid, and NMP being more preferred. These solvents can be used alone or in mixtures of two or more solvents.

[0085] In the method of removing oligomers under reduced pressure, the reaction can be carried out under heating as needed within a pressure range of 0.001 atm to 1 atm after the reaction is completed.

[0086] The polyether nitrile particles of the present invention can be obtained by precipitating polyether nitrile particles from a solution in which the polyether nitrile of the present invention is dissolved. This process is called particle formation. At this time, solid polyether nitrile can be dissolved in an organic solvent and then the polyether nitrile can be particled from that solution. However, in order to reduce the number of steps, it is preferable to directly perform the particle formation of polyether nitrile from the reaction mixture in which the polyether nitrile obtained by the above operation is dissolved.

[0087] As a method for precipitating polyether nitrile particles during the manufacture of the polyether nitrile particles of the present invention, polyether nitrile particles can be obtained by discharging the polyether nitrile solution into a mixture of a good solvent and a bad solvent.

[0088] As a good solvent for polyether nitrile, there are no restrictions on any solvent capable of dissolving polyether nitrile, including solvents that can dissolve polyether nitrile upon heating. Specific examples of such solvents include nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolium ketone (DMI), hexamethylphosphoramide, and tetramethylurea; sulfoxide / sulfone solvents such as dimethyl sulfoxide (DMSO), dimethyl sulfone, diphenyl sulfone, and sulfolane; nitrile solvents such as benzyl nitrile, diaryl ethers such as diphenyl ether, ketones such as benzophenone and acetophenone; and mixtures thereof. In the case of particle formation of polyether nitrile from the reaction mixture, solvents selected from NMP, DMSO, and sulfolane, which are also particularly preferred as reaction solvents, are preferred.

[0089] As a poor solvent, there are no limitations as long as it is a good solvent that can be mixed with the aforementioned polyether nitrile and cannot dissolve the polyether nitrile. Specifically, methanol, water, etc. are preferred examples.

[0090] For example, polyether nitrile particles can be formed by draining the reaction solution after the reaction is complete into a receiving container filled with a mixed solvent of NMP:water = 8:2 (volume ratio). In this case, the number-average particle size of the obtained polyether nitrile particles can be controlled by adjusting the type and composition of the solvent. For example, by reducing the proportion of water, particles with a smaller number-average particle size can be produced.

[0091] In addition, particles with a target number-average particle size can also be produced by crushing the particles or polymer blocks obtained through such operations.

[0092] Example

[0093] The invention is illustrated below with specific examples. These examples are exemplary and not limiting.

[0094] <Proton NMR Measurement>

[0095] Proton NMR measurements were performed using a JNM-ECZ-500R (manufactured by JEOL Ltd.), with the sample dissolved in a mixed solvent of pentafluorophenol / deuterated chloroform = 5 / 4 (volume ratio). The integral values ​​of peak A and B, representing the final peak (integral value of peak (A+C)) and the integral value of peak B, were calculated from the obtained spectra.

[0096] Peak A: A peak with a apex in the range of 7.10–7.20 ppm.

[0097] Peak B: A peak with a apex in the range of 7.55–7.68 ppm.

[0098] Peak C: A peak with a apex in the range of 6.95 to 7.00 ppm.

[0099] Melting point

[0100] The melting point is determined by differential scanning calorimetry (DSC). DSC determination uses... The process was conducted using Q20. The temperature was increased from 50°C to 400°C at a rate of 20°C / min, held at 400°C for 1 minute, then decreased from 400°C to 50°C at a rate of 20°C / min. The temperature was then increased again from 50°C to 400°C at a rate of 20°C / min, held at 400°C for 1 minute, and then decreased from 400°C to 100°C at a rate of 20°C / min. The melting point was the value obtained during the second heating.

[0101] <Thermogravimetric Analysis (TG)>

[0102] The weight loss rate when held at melting point +30°C for 30 minutes. The weight loss was measured using the company-manufactured TGA7. After being held at 50°C for 1 minute in an airflow, the temperature was raised to the melting point +30°C and held at the melting point +30°C for 30 minutes. The weight loss rate was then calculated based on the weight after holding at 50°C for 1 minute.

[0103] Melt viscosity

[0104] The viscosity rise rate was measured using a rheometer. The rheometer uses... The viscosity was measured using a Physica MCR501 micrometer with an amplitude of 1000 Pa and an angular frequency of 6.28 rad / s. The sample was kept in air at its melting point of +30°C for 30 minutes, and the viscosity increase rate was calculated from the change in melt viscosity before and after heating.

[0105] <Number-average particle size of polyethernitrile particles>

[0106] The number-average particle size of polyether nitrile particles is calculated by observing the shape under a microscope. Microscope usage... The VHX-S650 microscope measures the diameter of 100 randomly selected particles from a microscope image viewed at 100x magnification, and calculates the average diameter. In cases where the particle shape is not perfectly spherical, the longest and shortest diameters are measured, and their average is taken as the particle diameter.

[0107] <Raw materials used in the examples>

[0108] • Hydroquinone ( Co., Ltd.)

[0109] • Resorcinol ( Co., Ltd.)

[0110] ･4,4'-Dihydroxybiphenyl Co., Ltd.)

[0111] ･2,6-Dichlorobenzylnitrile ( Co., Ltd.)

[0112] Sodium carbonate ( Co., Ltd.)

[0113] ･NMP( Co., Ltd.).

[0114] [Example 1]

[0115] In a 300 mL separable flask equipped with a stirrer, nitrogen inlet tube, and Dean-Stark tube, 8.81 g (80.0 mmol) of hydroquinone, 13.93 g (81.0 mmol) of 2,6-dichlorobenzyl nitrile, and 10.18 g (96.0 mmol) of sodium carbonate were added. Under a nitrogen atmosphere, 80 mL of NMP and 3 mL of toluene were added, and the mixture was reacted at 160 °C for 0.5 h, followed by 8 h at 200 °C. After the reaction was complete, the reaction solution was drained into a receiving container containing 300 mL of a mixed solvent of NMP:water = 8:2 (volume ratio), thus granulating the polyether nitrile. The resulting polyether nitrile particles were washed three times with 300 mL of a mixed solvent of NMP:water = 8:2 (volume ratio) at room temperature, and then three times with 300 mL of warm water (80 °C). The particles were then vacuum dried overnight at 80 °C to obtain 13.6 g of white polyether nitrile particles.

[0116] Proton NMR measurements were performed, and the results showed a peak from the hydroxyl terminus (peak A) at 7.11–7.13 ppm, a peak from the benzyl nitrile backbone of the main chain at 7.59–7.62 ppm (peak B), and a peak from the chlorine terminus (peak C) at 6.97–6.99 ppm. The integral values ​​of peak A / peak B and (A+C) / peak B were calculated from these integral values. The obtained polyether nitrile was analyzed, and the integral values ​​of peak A / peak B, (A+C) / peak B, melting point, weight loss in air, viscosity increase in air, and number-average particle size are shown in Table 1.

[0117] [Examples 2-9, Comparative Examples 1-6]

[0118] The types and amounts of the aromatic compounds substituted with two hydroxyl groups, the amount of 2,6-dichlorobenzyl nitrile, the amount of sodium carbonate, and the polymerization time (holding time after reaching 200°C) were varied as shown in Tables 1 and 2. Otherwise, the same procedures as in Example 1 were performed. The resulting polyether nitrile particles were analyzed, and the integral values ​​of peak A / peak B, peak (A+C) / peak B, melting point, weight loss in air, viscosity increase in air, and number-average particle size are shown in Tables 1 and 2.

[0119] [Table 1]

[0120]

[0121] [Table 2]

[0122]

[0123] [Example 10]

[0124] The particles obtained in Example 1 were pulverized using a reverse jet mill to produce polyether nitrile particles with a number average particle size of 1.2 μm. Analysis of the obtained polyether nitrile particles revealed that the integral values ​​of peak A / peak B, peak (A+C) / peak B, melting point, weight loss in air, and viscosity increase in air were identical to those of the polyether nitrile particles obtained in Example 1.

[0125] [Example 11]

[0126] The post-polymerization treatment method was changed as follows: the reaction solution was drained into a receiving container containing 300 mL of a mixed solvent of NMP:water = 6:4 (volume ratio) to granulate the polyether nitrile. The resulting polyether nitrile particles were washed three times with 300 mL of a mixed solvent of NMP:water = 8:2 (volume ratio) at room temperature, and then washed three times with 300 mL of warm water (80°C). The particles were then vacuum-dried overnight at 80°C. Otherwise, the same procedures as in Example 1 were performed. Analysis of the obtained polyether nitrile particles showed that the integral value of peak A / peak B, the integral value of peak (A+C) / peak B, the melting point, the weight loss rate under air, and the viscosity increase rate under air were identical to those obtained in Example 1. The number-average particle size of the polyether nitrile particles was 180 μm.

[0127] As can be seen from the results of Examples 1 to 9, the thermal stability (weight loss rate in air, viscosity increase rate in air) is superior compared with Comparative Examples 1 to 6, which have a range of "integral value of peak A / integral value of peak B" of less than 0.050.

[0128] On the other hand, as shown in Comparative Examples 1 to 5, when the types and amounts of aromatic compounds substituted with two hydroxyl groups and the amount of 2,6-dichlorobenzyl nitrile are the same, there is a tendency for the "integral value of peak A / integral value of peak B" to be greater than 0.050.

[0129] It should be noted that Comparative Example 6 is a comparative example equivalent to Example 1 of International Publication No. WO2021 / 21492, and the integral value of peak A / integral value of peak B is greater than 0.050. It can be seen that compared with Comparative Example 6, Examples 7 and 8 of this application have a smaller integral value of peak A / integral value of peak B and excellent thermal stability (weight loss rate in air, viscosity increase rate in air).

Claims

1. A polyether nitrile, as shown in formula (I), wherein in proton NMR measurements using a mixed solvent of pentafluorophenol and deuterated chloroform at a volume ratio of 5:4, the ratio of the integral value of peak A to the integral value of peak B is 0.050 or less. Peak A: A peak with a apex in the range of 7.10–7.20 ppm. Peak B: A peak with a apex in the range of 7.55–7.68 ppm. In equation (I), Ar is any of the units represented by equations (a) to (f), and Ar can be composed of one or more types of units. 。 2. In the proton NMR determination of the polyether nitrile according to claim 1, using a mixed solvent of pentafluorophenol and deuterated chloroform in a volume ratio of 5:4, the integral value of the terminal peak / the integral value of peak B is 0.001~0.

055.

3. The polyether nitrile according to claim 1 or 2, wherein Ar is composed of two or more units.

4. A polyether nitrile particle formed from the polyether nitrile according to claim 1 or 2, wherein the number-average particle size of the polyether nitrile particle is 0.1 to 200 μm.

5. A component for a moving body comprising the polyether nitrile as described in claim 1 or 2.

6. A structural material component comprising the polyether nitrile as described in claim 1 or 2.

7. A component for electrical / electronic materials comprising the polyether nitrile as described in claim 1 or 2.

8. A mobile body that uses the mobile body component as described in claim 5.

9. A structural material that uses a structural material component as described in claim 6.

10. An electrical / electronic product that uses a component made of the electrical / electronic material as described in claim 7.

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