Method for producing aromatic heterocyclic polymer powders

Abstract

This disclosure belongs to the field of polymer materials technology and specifically provides a method for producing aromatic heterocyclic polymer powders. [Solution] The manufacturing method provided in this disclosure is a method for producing aromatic heterocyclic polymer powder, comprising the steps of simultaneously cooling and shearing an aromatic heterocyclic polymer solution to obtain the aromatic heterocyclic polymer powder, wherein the initial temperature of the cooling is 200 to 250°C and the target temperature is -20 to 50°C, and the solvent of the aromatic heterocyclic polymer solution is sulfolane. By performing the cooling and shearing treatment simultaneously, the aromatic ring polymer mixture is subdivided during the phase transition process and directly produced as aromatic ring polymer powder or powder sheet with a uniform morphology and a narrow particle size distribution. This method avoids mechanical impurities caused by mechanical friction during the crushing and grinding processes in conventional processes, allowing for the direct acquisition of pure powder and improving product quality.

Description

Technical Field

[0001] The present disclosure belongs to the technical field of polymer materials, and specifically relates to a method for manufacturing aromatic heterocyclic polymer powder.

Background Art

[0002] An aromatic heterocyclic polymer is a polymer whose main polymer chain is mainly composed of a heterocyclic ring or an aromatic heterocyclic ring structure. Such polymers have excellent properties such as high heat resistance, high strength, high elastic modulus, excellent electrical insulation, and excellent radiation resistance and chemical media corrosion resistance. Due to its excellent properties, aromatic heterocyclic polymers show broad application prospects in various fields such as the electronics industry, construction industry, automotive industry, chemical industry, aerospace and pharmaceutical industries.

[0003] Currently, when processing aromatic heterocyclic polymers, usually, the methods of dispersion and pulverization are sequentially used. Specifically, by the method of pressure or natural flow, it is stretched into thin strips in a dispersant, or enters the dispersant by natural dropping or pressure injection through a sieve plate, and after being solidified into spherical-like solids, it becomes a sheet-like, granular or块状 powder product through the treatment by a crusher and a pulverizer. However, the products obtained by the above methods have different particle sizes, and the particle size distribution range is as wide as 0.1 - 1000 μm, resulting in disadvantages such as low washing efficiency, difficulty in removing residues, and small bulk density.

Summary of the Invention

Problems to be Solved by the Invention

[0004] The object of the present disclosure is to provide a method for manufacturing an aromatic heterocyclic polymer powder with a uniform morphology and a narrow particle size distribution range.

Means for Solving the Problems

[0005] To achieve the above object, the present disclosure provides the following aspects.

[0006] This disclosure provides a method for producing aromatic heterocyclic polymer powder, comprising the steps of simultaneously cooling and shearing an aromatic heterocyclic polymer solution to obtain the aromatic heterocyclic polymer powder, wherein the cooling has an initial temperature of 200 to 250°C, a target temperature of -20 to 50°C, and the solvent of the aromatic heterocyclic polymer solution is sulfolane.

[0007] The aromatic heterocyclic polymer in the aromatic heterocyclic polymer solution preferably comprises one or more of the following: polyethersulfone, polyetheretherketone, and polymer A, wherein polymer A has the configuration represented by formula 1. [ka] Here, R1 and R2 independently comprise one or more of the following: halogen, amino group, hydroxyl group, alkyl group, alkenyl group, alkynyl group, aryl group, ether group, thioether group, carboxyl group, ester group, amide group, imide group, alkali metal sulfonic acid base, alkyl sulfonic acid ester group, alkyl phosphate ester group, amine group, and quaternary ammonium group, and e is an integer from 0 to 4.

[0008] The polymer A preferably contains polyphenylene sulfone (PPSU) and / or polysulfone.

[0009] The content of the aromatic heterocyclic polymer in the aromatic heterocyclic polymer solution is preferably 5 to 50% by mass.

[0010] The aromatic heterocyclic polymer solution further comprises a salt and / or a base, The content of the salt and / or base is preferably 5 to 15% by mass.

[0011] The shearing is preferably performed with a motor frequency of 10 to 100 Hz and a duration of 10 to 120 minutes.

[0012] The cooling rate is preferably 5 to 30°C / min.

[0013] The above-mentioned manufacturing method further comprises the step of mixing the aromatic heterocyclic polymer solution with a dispersant, wherein the dispersant preferably contains one or more of water, liquid alcohol, liquid ether, and liquid ester.

[0014] The liquid alcohol comprises one or more of methanol, ethanol, and isopropyl alcohol. The liquid ether comprises one or more of methyl ether, ethyl ether, n-propyl ether, and isopropyl ether. The liquid ester preferably contains one or more of ethyl formate, ethyl acetate, and butyl propionate.

[0015] The mass ratio of the dispersant to the aromatic heterocyclic polymer solution is 1:1 to 10. The mixing temperature is preferably between 0 and 150°C. [Effects of the Invention]

[0016] This disclosure provides a method for producing an aromatic heterocyclic polymer powder, comprising the steps of simultaneously cooling and shearing an aromatic heterocyclic polymer solution to obtain the aromatic heterocyclic polymer powder, wherein the cooling has an initial temperature of 200 to 250°C and a target temperature of -20 to 50°C, and the solvent of the aromatic heterocyclic polymer solution is sulfolane. The manufacturing method provided in this disclosure replaces conventional pelletizing, stripping, crushing, and pulverizing processes with simultaneous cooling and shearing. As the temperature of the system gradually decreases, the viscosity of the polymer gradually increases, and the state changes from a complete liquid to a solid-liquid mixture, and then to a solid. During the phase transition process, the mixture is subdivided, directly producing an aromatic ring polymer mixture as an aromatic ring polymer powder or powder sheet with a uniform morphology and a narrow particle size distribution. This avoids the problem of difficulty in removing residues and eliminates unnecessary washing caused by large particle size differences.

[0017] Furthermore, the manufacturing method provided in this disclosure avoids mechanical impurities caused by mechanical friction during the crushing and grinding processes in conventional methods, allowing for the direct acquisition of pure powder and improving product quality. On the other hand, the manufacturing method provided in this disclosure can produce powders with various particle size distribution ranges without the need for secondary processing such as polishing or grinding, depending on the application field. [Brief explanation of the drawing]

[0018] To more clearly illustrate the embodiments of this disclosure or the technical concepts in the existing art, the drawings necessary for the embodiments will be briefly described below. However, the drawings in the following description represent only a few of the embodiments of this disclosure, and it will be obvious to those skilled in the art that other drawings can be obtained based on these drawings without any creative effort.

[0019] [Figure 1] This figure compares existing technologies with the process flow of the method for producing aromatic heterocyclic polymer powders provided in this disclosure. [Figure 2] This is a physical diagram showing the initial state of the salt-containing polyethersulfone solution in Example 1. [Figure 3] This is a real-world diagram of the intermediate state when no dispersant is added to the salt-containing polyethersulfone solution in Example 1. [Figure 4] This is a physical diagram of the final product obtained in Example 1 when no dispersant was added to the salt-containing polyethersulfone solution. [Figure 5] It is a photograph of an intermediate state when ethanol is added as a dispersant to the salt-containing polyethersulfone solution in Example 2. [Figure 6] It is a photograph of the final product when ethanol is added as a dispersant to the salt-containing polyethersulfone solution in Example 2. [Figure 7] It is a photograph of an intermediate state when water is added as a dispersant to the salt-containing polyethersulfone solution in Example 3. [Figure 8] It is a photograph of the final product when water is added as a dispersant to the salt-containing polyethersulfone solution in Example 3. [Figure 9] It is a photograph of the initial state of the de-salted polyethersulfone solution in Example 7.

Embodiments for Carrying Out the Invention

[0020] The present disclosure provides a method for producing an aromatic heterocyclic polymer powder, comprising the step of simultaneously cooling and shearing an aromatic heterocyclic polymer solution to obtain the aromatic heterocyclic polymer powder, wherein the cooling has an initial temperature of 200 to 250 °C and a target temperature of -20 to 50 °C, and the solvent of the aromatic heterocyclic polymer solution is sulfolane.

[0021] In the present disclosure, unless otherwise specified, all raw material components are commercially available products well known to those skilled in the art.

[0022] In the present disclosure, the aromatic heterocyclic polymer in the aromatic heterocyclic polymer solution includes one or more of polyethersulfone, polyetheretherketone, and polymer A, and the polymer A has a structure represented by Formula 1.

Chemical Formula

[0023] In this disclosure, the content of the aromatic heterocyclic polymer in the aromatic heterocyclic polymer solution may be 5 to 50% by mass, and in specific examples, it may be 10%, 20%, 35%, or 45%. In this disclosure, the above range is preferred for the content of the aromatic heterocyclic polymer in the aromatic heterocyclic polymer solution, because in solvent-based polymerization, it is easier to handle the apparatus if the polymer content does not exceed the solvent content. If the polymer content is too high, for example, the fluidity will be poor, which will be disadvantageous for post-treatment. Also, solvent-free polymerization is rarely employed.

[0024] In this disclosure, the aromatic heterocyclic polymer solution may be an aromatic heterocyclic polymer heavy solution, an aromatic heterocyclic polymer product system, or a desalted aromatic heterocyclic polymer product system. When the aromatic heterocyclic polymer solution is an aromatic heterocyclic polymer product system, the aromatic heterocyclic polymer solution may further contain salts and / or bases. The salts include organic salts and / or inorganic salts. The organic salts include, for example, sodium phenol salts and / or potassium phenol salts. The inorganic salts are, for example, alkali metal inorganic salts. The inorganic salts include, for example, one or more of sodium bicarbonate, potassium bicarbonate, potassium carbonate, and sodium carbonate. The bases include, for example, sodium hydroxide and / or potassium hydroxide. The content of salts and / or bases in the aromatic heterocyclic polymer solution is, for example, 5 to 15% by mass, and in specific examples, it may be 6%, 9%, or 12%. The desalted aromatic heterocyclic polymer product system in this disclosure is a system comprising the remaining mixture after polymerization, from which the salt produced by the reaction in the polyaryl ether sulfone resin mixture and the unreacted salt have been removed by a filtration device, and the pure aromatic heterocyclic polymer dissolved in sulfolane.

[0025] In this disclosure, the method for producing the aromatic heterocyclic polymer product system includes the step of mixing aromatic dihydroxy, aromatic dihalogen, an alkaline reagent, and sulfolane to carry out a polymerization reaction to obtain the aromatic heterocyclic polymer product system.

[0026] In this disclosure, the aromatic dihydroxyl may include one or more of hydroquinone, catechol, resorcinol, bis(hydroxyphenyl)alkane, dihydroxydiphenylsulfone, 4,4'-biphenyldinol, and dihydroxydiphenyl ether, and in specific examples, it may be 4,4-dihydroxydiphenylsulfone. The aromatic dihalogen may include 4,4'-dichlorodiphenylsulfone and / or 4,4'-difluorodiphenylsulfone, and in specific examples, it may be 4,4'-dichlorodiphenylsulfone. The molar ratio of the aromatic dihydroxyl to the aromatic dihalogen may be 1 to 1.3, and in specific examples, it may be 1.02, 1.1, or 1.15. The alkaline reagent may include an alkali metal inorganic salt and / or a base, and the alkali metal inorganic salt may include one or more of sodium bicarbonate, potassium bicarbonate, potassium carbonate, and sodium carbonate, and the base may include sodium hydroxide and / or potassium hydroxide. The molar ratio of the alkaline reagent to the elemental aromatic dihydroxy may be 1 to 2.5, and in specific examples, it may be 1.3, 1.5, 1.8, or 2.

[0027] In this disclosure, the polymerization reaction temperature is 200 to 240°C, and in specific embodiments, it may be 220°C. The duration is 4 to 9 hours, and in specific embodiments, it may be 6 hours or 8 hours.

[0028] In this disclosure, the method for producing the desalted aromatic heterocyclic polymer product system includes the step of mixing aromatic dihydroxy, aromatic dihalogen, an alkaline reagent, and sulfolane, and sequentially carrying out polymerization and desalting treatments to obtain the desalted aromatic heterocyclic polymer product system.

[0029] In this disclosure, the raw materials and reaction conditions for the polymerization reaction are the same as described above, so they are omitted here.

[0030] In this disclosure, the motor frequency for shearing is 10 to 100 Hz, and in specific embodiments, it may be 40 Hz, 60 Hz, or 80 Hz. The duration is 10 to 120 minutes, and in specific embodiments, it may be 30 minutes, 50 minutes, 80 minutes, or 100 minutes. If the temperature of the aromatic heterocyclic polymer solution is 100 to 250°C, the shearing may be carried out in a nitrogen gas atmosphere or an inert gas atmosphere. If the temperature of the aromatic heterocyclic polymer solution is -20 to 100°C, the shearing may be carried out in a nitrogen atmosphere, an inert gas atmosphere, or an air atmosphere. The atmospheric pressure of the nitrogen gas environment, inert gas environment, or air environment may be normal pressure. The apparatus for carrying out the shearing may be a kneader, a compounding machine, a kneader extruder, or an extruder. The ratio of the volume of the aromatic heterocyclic polymer solution to the cavity volume of the apparatus for carrying out the shearing may be 1:1 to 10, and in specific embodiments, it may be 1:3 or 2:3. By employing the gas atmosphere described above, discoloration due to oxidation of the polymer can be prevented under temperature conditions exceeding 100°C.

[0031] In this disclosure, the initial cooling temperature may be 200 to 250°C, and in specific embodiments, it may be 220°C or 240°C. The target temperature may be -20 to 50°C, and in specific embodiments, it may be -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, or 50°C. The cooling rate may be 5 to 30°C / min, and in specific embodiments, it may be 10°C / min or 20°C / min. The cooling device may be an external circulation cooling device. The temperature of the external circulation cooling device may be -40 to 25°C, and in specific embodiments, it may be -20°C, 0°C, or 20°C.

[0032] The disclosure may further include a step of mixing an aromatic heterocyclic polymer solution with a dispersant. The dispersant may include one or more of water, liquid alcohol, liquid ether, and liquid ester. The liquid alcohol may include one or more of methanol, ethanol, and isopropanol. The liquid ether may include one or more of methyl ether, ethyl ether, n-propyl ether, and isopropyl ether. The liquid ester may include one or more of ethyl formate, ethyl acetate, and butyl propionate. In specific examples, the dispersant may be water and / or liquid alcohol. The mass ratio of the dispersant to the aromatic heterocyclic polymer solution may be 1:1 to 10, and in specific examples, the mass ratio of the dispersant to the aromatic heterocyclic polymer solution may be 1:2, 1:5, 1:8, or 1:1 to 10. The mixing temperature may be 0 to 150°C, and in specific examples, it may be 80°C, 100°C, or 120°C. In this disclosure, the function of the dispersant is to prevent the polymer from clumping together due to adhesion, which would make pulverization difficult.

[0033] This disclosure may further include washing and drying after shearing. The washing may be performed in a washing vessel. The reagent for washing may be water. The number of washes may be 4 to 10, and in specific examples, it may be 6. The time for each wash is 1 to 3 hours, and in specific examples, it may be 1.5 hours. The drying may be performed under negative pressure.

[0034] In this disclosure, the aromatic heterocyclic polymer powder may be in granular or sheet form. The particle size of the aromatic heterocyclic polymer powder may be 1000 μm or less. If the aromatic heterocyclic polymer powder is in flake form, the particle size may be 600 to 1000 μm, and in specific examples, it may be 700 μm, 800 μm, or 900 μm. If the aromatic heterocyclic polymer powder is in granular form, the particle size may be 200 μm or less, and in specific examples, it may be 50 μm, 100 μm, or 150 μm. The aromatic heterocyclic polymer powder may have an ash content of less than 0.3%, a bulk density of 0.3 to 0.6 g / mL, and a solvent residue of less than 0.05%.

[0035] The manufacturing method provided in this disclosure replaces conventional pelletizing, stripping, crushing, and pulverizing processes with simultaneous cooling and shearing. As the temperature of the system gradually decreases, the viscosity of the polymer gradually increases, and the state changes from a complete liquid to a solid-liquid mixture, and then to a solid. In the phase transition process, it is subdivided, and the aromatic ring polymer mixture can be directly produced as an aromatic ring polymer powder or powder sheet with a uniform morphology and a narrow particle size distribution. As a result, the surface of the resulting product is sparse and easy to clean, thus avoiding the problem of difficulty in removing residues, and eliminating unnecessary cleaning caused by large particle size differences.

[0036] Furthermore, the manufacturing method provided in this disclosure avoids mechanical impurities caused by mechanical friction during the crushing and grinding processes in conventional methods, allowing for the direct acquisition of pure powder and improving product quality. On the other hand, the manufacturing method provided in this disclosure can produce powders with various particle size distribution ranges without the need for secondary processing such as polishing or grinding, depending on the application field.

[0037] To further illustrate this disclosure, the methods for producing aromatic heterocyclic polymer powders provided in this disclosure will be described in detail below with reference to the drawings, but these should not be construed as limiting the scope of protection of this disclosure.

[0038] Figure 1 is a diagram comparing the process flow of an existing technology with the method for producing aromatic heterocyclic polymer powder provided in this disclosure. As can be seen from Figure 1, this disclosure simplifies the number of steps by using a high-shear device instead of a dispersion device, crushing device, and grinding device, and by performing the equivalent of three steps in one step, it is possible to avoid contamination during the process and reduce costs. [Examples]

[0039] In embodiments of the present disclosure, unless otherwise specified, the rotational speed of the kneader is set to 45 Hz, and the cooling rate is determined by a cooling circulation device and set to 10°C / min.

[0040] [Comparative Example 1] 4,4-Dihydroxydiphenylsulfone 2552.7581 g (10.02 mol), 4,4'-Dichlorodiphenylsulfone 2871.600 g (10.00 mol), sodium carbonate 1621.647 g (15.3 mol), and sulfolane 10836.709 g (90.2 mol) were placed in a 30,000 ml polymerization vessel. After replacing the air with nitrogen gas three times, the temperature was raised to 235°C under nitrogen gas protection and the reaction was carried out for 8 hours to obtain a salt-containing polyethersulfone product system with a solid content of 30%. This was dispersed in strip form in pure water, and then sequentially treated by mechanical crushing and mechanical grinding, washed with pure water six times, and dried under negative pressure to obtain a powder.

[0041] [Example 1] After obtaining a salt-containing polyethersulfone product system according to the manufacturing method of Comparative Example 1, a kneader with a cavity volume of 5 L and an external cooling circulation device set to 5°C were started. After replacing the air with nitrogen gas three times, the nitrogen gas atmosphere was maintained, and 3 L of the salt-containing polyethersulfone product system with a solid content of 30% was introduced into the kneader cavity. When the temperature dropped to 35°C, the material in the cavity hardened and crushed into a powder. The obtained powder was washed with pure water six times and dried under negative pressure to obtain a pure powder.

[0042] [Example 2] After obtaining a salt-containing polyethersulfone product system according to the manufacturing method of Comparative Example 1, a kneader with a cavity volume of 5 L and an external cooling circulation device set to 5°C were started. After replacing the air with nitrogen gas three times, the nitrogen gas atmosphere was maintained, and 3 L of the salt-containing polyethersulfone product system with a solid content of 30% was added to the kneader cavity. When the temperature dropped to 120°C, ethanol was added through piping. The mass ratio of ethanol to the salt-containing polyethersulfone product system was 1:10. When the temperature dropped to 30°C, the material in the cavity hardened and crumbled into a powder. The obtained powder was washed with pure water six times and dried under negative pressure to obtain a pure powder.

[0043] [Example 3] After obtaining a salt-containing polyethersulfone product system according to the manufacturing method of Comparative Example 1, a kneader with a cavity volume of 5 L and an external cooling circulation device set to 5°C were started. After replacing the air with nitrogen gas three times, the nitrogen gas atmosphere was maintained, and 3 L of the salt-containing polyethersulfone product system with a solid content of 30% was added to the kneader cavity. When the temperature dropped to 120°C, water was added through piping. The mass ratio of water to the salt-containing polyethersulfone product system was 1:2. When the temperature dropped to 45°C, the material in the cavity hardened and crumbled into powder. The obtained powder was washed with pure water six times and dried under negative pressure to obtain a pure powder.

[0044] [Comparative Example 2] 1899.3420 g (10.02 mol) of 4,4'-biphenyldinol, 2871.600 g (10.00 mol) of 4,4'-dichlorodiphenylsulfone, 1621.647 g (15.3 mol) of sodium carbonate, and 9428.8647 g (78.46 mol) of sulfolane were placed in a 30,000 ml polymerization vessel. After replacing the air with nitrogen gas three times, the temperature was raised to 230°C under nitrogen gas protection and the reaction was carried out for 8 hours to obtain a salt-containing polyphenylene sulfone product system with a solid content of 30%. This was dispersed in strip form in pure water, and then sequentially treated by mechanical crushing and mechanical grinding, washed with pure water six times, and dried under negative pressure to obtain a powder.

[0045] [Example 4] After obtaining a salt-containing polyphenylene sulfone product system according to the manufacturing method of Comparative Example 2, a kneader with a cavity volume of 5 L and an external cooling circulation device set to 5°C were started. After replacing the air with nitrogen gas three times, the nitrogen gas atmosphere was maintained, and 3 L of the salt-containing polyphenylene sulfone product system with a solid content of 30% was introduced into the kneader cavity. When the temperature dropped to 40°C, the material in the cavity hardened and crushed into a powder. The obtained powder was washed with pure water six times and dried under negative pressure to obtain a pure powder.

[0046] [Example 5] After obtaining a salt-containing polyphenylene sulfone product system according to the manufacturing method of Comparative Example 2, a kneader with a cavity volume of 5 L and an external cooling circulation device set to -5°C were started. After replacing the air with nitrogen gas three times, the nitrogen gas atmosphere was maintained, and 3 L of the salt-containing polyphenylene sulfone product system with a solid content of 30% was introduced into the cavity of the kneader. When the temperature dropped to 120°C, ethanol was added through piping. The mass ratio of ethanol to the salt-containing polyphenylene sulfone product system was 1:10. When the temperature dropped to 37°C, the material in the cavity hardened and crumbled into a powder. The obtained powder was washed with pure water six times and dried under negative pressure to obtain a pure powder.

[0047] [Example 6] After obtaining a salt-containing polyphenylene sulfone product system according to the manufacturing method of Comparative Example 2, a kneader with a cavity volume of 5 L and an external cooling circulation device set to 5°C were started. After replacing the air with nitrogen gas three times, the nitrogen gas atmosphere was maintained, and 3 L of the salt-containing polyphenylene sulfone product system with a solid content of 30% was introduced into the cavity of the kneader. When the temperature dropped to 120°C, water was added through piping. The mass ratio of water to the salt-containing polyphenylene sulfone product system was 1:2. When the temperature dropped to 48°C, the material in the cavity hardened and crumbled into powder. The obtained powder was washed with pure water six times and dried under negative pressure to obtain a pure powder.

[0048] [Comparative Example 3] 2552.7581 g (10.02 mol) of 4,4-dihydroxydiphenylsulfone, 2871.600 g (10.00 mol) of 4,4'-dichlorodiphenylsulfone, 1621.647 g (15.3 mol) of sodium carbonate, and 10836.709 g (90.2 mol) of sulfolane were placed in a 30,000 ml polymerization vessel. After replacing the air with nitrogen gas three times, the temperature was raised to 235°C under nitrogen gas protection and the reaction was carried out for 8 hours to obtain a salt-containing polyethersulfone product system. Subsequently, the salt was removed from the product system using a pressurized desalination filter to obtain a desalted polyethersulfone product system with a solid content of 35%. This was dispersed in strip form in pure water, and then sequentially treated by mechanical crushing and mechanical grinding, washed with pure water six times, and dried under negative pressure to obtain a powder.

[0049] [Example 7] Following the manufacturing method of Comparative Example 3, a desalted polyethersulfone product system with a solid content of 35% was obtained. Then, a kneader with a cavity volume of 5 L and an external cooling circulation device set to 5°C were started. After replacing the air with nitrogen gas three times, the nitrogen gas atmosphere was maintained, and 3 L of the desalted polyethersulfone product system with a solid content of 35% was introduced into the cavity of the kneader. As the temperature dropped to 35°C, the material in the cavity hardened and crushed into a powder. The obtained powder was washed with pure water six times and then dried under negative pressure to obtain a pure powder.

[0050] [Example 8] Following the manufacturing method of Comparative Example 3, a desalted polyethersulfone product system with a solid content of 35% was obtained. Then, a kneader with a cavity volume of 5 L and an external cooling circulation device set to -5°C were started. After replacing the air with nitrogen gas three times, the nitrogen gas atmosphere was maintained, and 3 L of the desalted polyethersulfone product system with a solid content of 35% was introduced into the cavity of the kneader. When the temperature dropped to 120°C, ethanol was added through piping. The mass ratio of ethanol to the desalted polyethersulfone product system was 1:10. When the temperature dropped to 30°C, the material in the cavity hardened and crumbled into powder. The obtained powder was washed with pure water six times and dried under negative pressure to obtain a pure powder.

[0051] [Example 9] Following the manufacturing method of Comparative Example 3, a desalted polyethersulfone product system with a solid content of 35% was obtained. Then, a kneader with a cavity volume of 5 L and an external cooling circulation device set to 5°C were started. After replacing the air with nitrogen gas three times, the nitrogen gas atmosphere was maintained, and 3 L of the desalted polyethersulfone product system with a solid content of 35% was introduced into the cavity of the kneader. When the temperature dropped to 120°C, water was added through piping. The mass ratio of water to the desalted polyethersulfone product system was 1:2. When the temperature dropped to 45°C, the material in the cavity hardened and crumbled into powder. The obtained powder was washed with pure water six times and dried under negative pressure to obtain a pure powder.

[0052] [Comparative Example 4] 1899.3420 g (10.02 mol) of 4,4'-biphenyldinol, 2871.600 g (10.00 mol) of 4,4'-dichlorodiphenylsulfone, 1621.647 g (15.3 mol) of sodium carbonate, and 9428.8647 g (78.46 mol) of sulfolane were placed in a 30,000 ml polymerization vessel. After replacing the air with nitrogen gas three times, the temperature was raised to 230°C under nitrogen gas protection and the reaction was carried out for 8 hours to obtain a salt-containing polyphenylene sulfone product system. Subsequently, the salt was removed from the product system using a pressurized desalination filter to obtain a desalted polyphenylene sulfone product system with a solid content of 35%. This was dispersed in strip form in pure water, and then sequentially treated by mechanical crushing and mechanical grinding, washed with pure water six times, and dried under negative pressure to obtain a powder.

[0053] [Example 10] After obtaining a desalted polyphenylene sulfone product system according to the manufacturing method of Comparative Example 4, a kneader with a cavity volume of 5 L and an external cooling circulation device set to 5°C were started. After replacing the air with nitrogen gas three times, the nitrogen gas atmosphere was maintained, and 3 L of desalted polyphenylene sulfone resin with a solid content of 35% was introduced into the kneader cavity. When the temperature dropped to 35°C, the material in the cavity hardened and crushed into a powder. The obtained powder was washed with pure water six times and dried under negative pressure to obtain a pure powder. For this pure powder, data on solvent residue, ash content, particle size distribution, and bulk density were measured.

[0054] [Example 11] After obtaining a desalted polyphenylene sulfone product system according to the manufacturing method of Comparative Example 4, a kneader with a cavity volume of 5 L and an external cooling circulation device set to 5°C were started. After replacing the air with nitrogen gas three times, the nitrogen gas atmosphere was maintained, and 3 L of desalted polyphenylene sulfone resin with a solid content of 35% was introduced into the cavity of the kneader. When the temperature dropped to 120°C, ethanol was added through piping. The mass ratio of ethanol to the desalted polyphenylene sulfone resin solution was 1:10. When the temperature dropped to 30°C, the material in the cavity hardened and crumbled into powder. The obtained powder was washed with pure water six times and dried under negative pressure to obtain a pure powder. For the pure powder, data on solvent residue, ash content, particle size distribution, and bulk density were measured.

[0055] [Example 12] After obtaining a desalted polyphenylene sulfone product system according to the manufacturing method of Comparative Example 4, a kneader with a cavity volume of 5 L and an external cooling circulation device set to 5°C were started. After replacing the air with nitrogen gas three times, the nitrogen gas atmosphere was maintained, and 3 L of desalted polyphenylene sulfone resin with a solid content of 35% was introduced into the kneader cavity. When the temperature dropped to 120°C, water was added through piping. The mass ratio of water to the desalted polyphenylene sulfone resin solution was 1:2. When the temperature dropped to 45°C, the material in the cavity hardened and crumbled into powder. The obtained powder was washed with pure water six times and dried under negative pressure to obtain pure powder. For the pure powder, data on solvent residue, ash content, particle size distribution, and bulk density were measured.

[0056] [Comparative Example 5] Polysulfone resin powder with a particle size of 300 μm or more was completely dissolved in sulfolane at 160°C to prepare 3 L of a desalted polysulfone resin solution with a solid content of 30%. This solution was then dispersed in strip form in pure water, and subsequently subjected to mechanical crushing and mechanical grinding, followed by six repeated washes with pure water and negative pressure drying to obtain the powder.

[0057] [Example 13] A kneader with a cavity volume of 5 L and an external cooling circulation device set to 5°C were started, and the air was replaced three times with nitrogen gas. After maintaining the nitrogen gas atmosphere, 3 L of a desalted polysulfone resin solution with a solid content of 30%, prepared in the same manner as in Comparative Example 5, was poured into the cavity of the kneader. When the temperature dropped to 35°C, the material in the cavity hardened and broke down into powder. The obtained powder was washed with pure water six times and dried under negative pressure to obtain pure powder.

[0058] [Example 14] A kneader with a cavity volume of 5 L and an external cooling circulation device set to 5°C were started. After replacing the air with nitrogen gas three times, the nitrogen gas atmosphere was maintained, and 3 L of a desalted polysulfone resin solution with a solid content of 30%, prepared in the same manner as in Comparative Example 5, was poured into the cavity of the kneader. When the temperature dropped to 120°C, ethanol was added through piping. The mass ratio of ethanol to the desalted polyethersulfone resin solution was 1:10. When the temperature dropped to 30°C, the material in the cavity hardened and broke down into a powder. The obtained powder was washed with pure water six times and dried under negative pressure to obtain a pure powder.

[0059] [Example 15] A kneader with a cavity volume of 5 L and an external cooling circulation device set to 5°C were started. After replacing the air with nitrogen gas three times, the nitrogen gas atmosphere was maintained, and 3 L of a desalted polysulfone resin solution with a solid content of 30%, prepared in the same manner as in Comparative Example 5, was poured into the cavity of the kneader. When the temperature dropped to 120°C, water was added through piping. The mass ratio of water to the desalted polyethersulfone resin solution was 1:2. When the temperature dropped to 45°C, the material in the cavity hardened and broke down into powder. The obtained powder was washed with pure water six times and dried under negative pressure to obtain pure powder.

[0060] In the examples of this disclosure, the aromatic heterocyclic polymers exhibited the same appearance in their dissolved state in the sulfolane system and the same state change in the kneader, thus allowing the same effects to be obtained using similar processing methods. Figure 2 is an actual diagram of the initial state of the salt-containing polyethersulfone solution in Example 1, and Examples 2-6 were consistent with it. Figure 3 is an actual diagram of the intermediate state of the salt-containing polyethersulfone solution in Example 1 when no dispersant was added, and Examples 4, 7, 10, and 13 were consistent with it. Figure 4 is an actual diagram of the final product of the salt-containing polyethersulfone solution in Example 1 when no dispersant was added, and Examples 4, 7, 10, and 13 were consistent with it. Figure 5 is an actual diagram of the intermediate state of the salt-containing polyethersulfone solution in Example 2 when ethanol was added as a dispersant, and Examples 5, 8, 11, and 14 were consistent with it. Figure 6 is an actual diagram of the final product of the salt-containing polyethersulfone solution in Example 2 when ethanol was added as a dispersant, and Examples 5, 8, 11, and 14 were consistent with it. Figure 7 is a real-world diagram of the intermediate state when water was added as a dispersant to the salt-containing polyethersulfone solution in Example 3, and Examples 6, 9, 12, and 15 were consistent with it. Figure 8 is a real-world diagram of the final product when water was added as a dispersant to the salt-containing polyethersulfone solution in Example 3, and Examples 6, 9, 12, and 15 were consistent with it. Figure 9 is a real-world diagram of the initial state of the desalted polyethersulfone solution in Example 7, and Examples 8 to 15 were consistent with it.

[0061] As can be seen from Figures 2-6, in the proposed technology provided in this disclosure, the salt-containing system and the desalted system of the aromatic heterocyclic polymer resin exhibited the same state in the kneader, except for the color. When kneading was performed for a certain period of time without adding a dispersant, the state shown in Figure 3 was observed. When 10% ethanol was added, granular polyethersulfone powder was gradually formed as the kneading time was extended. When water was added to a concentration of 50%, clumpy polyethersulfone powder was gradually formed as the kneading time was extended. Ultimately, in both cases, an aromatic heterocyclic polymer powder or powder sheet was formed.

[0062] Measurement example For Comparative Examples 1-5 and Examples 1-15, data on pulverization time, ash content, bulk density, solvent residue, and particle size distribution of the obtained powder products were measured. A thermogravimetric analyzer (TGA, TG Corporation, USA) was used to measure ash residue, a BT-100 general-purpose powder bulk density analyzer was used to measure bulk density, a gas chromatograph (Shimadzu Corporation, Japan) was used to measure solvent residue, and a laser particle size distribution analyzer (Zhuhai OMEC Instruments Co., Ltd.) was used to measure particle size distribution. These measurement results are shown in Table 1.

[0063] [Table 1]

[0064] As can be seen from Table 1, the proposed technology provided in this disclosure enabled the production of high-quality powder products, regardless of whether a dispersant was added or not. The particle size of the product decreased with the addition of ethanol additive, and changed from granular to thin clumps with the addition of water. This indicates that, in the proposed technology provided in this disclosure, regardless of the state of the polymer, it is possible to directly produce powder products in the desired state and with a narrow particle size distribution without requiring dispersion, shaping, crushing, and grinding processes.

[0065] As can be seen from the above examples, this disclosure innovates the processing process for aromatic heterocyclic polymers by using a shearing device and a circulating cooling device, and by utilizing the properties of aromatic heterocyclic polymers in sulfolane systems, thereby adjusting the solid content of the multi-ring polymer, the amount of dispersant, and the cooling temperature, and replacing some of the conventional processes. The powder products produced by this method do not require special processing, can meet market demands, significantly improve production efficiency, and achieve cost reduction and quality improvement.

[0066] The above embodiments illustrate the present disclosure in detail, but they represent only a portion of the embodiments of this disclosure, not all embodiments. Any other embodiments that can be easily conceived and obtained without departing from the spirit of this disclosure are all within the scope of protection of this disclosure. [Industrial applicability]

[0067] According to the present invention, a method for producing aromatic heterocyclic polymer powders with a uniform morphology and a narrow particle size distribution range is available.

Claims

1. A method for producing aromatic heterocyclic polymer powder, comprising the steps of simultaneously cooling and shearing an aromatic heterocyclic polymer solution to obtain the aromatic heterocyclic polymer powder, The manufacturing method is characterized in that the cooling has an initial temperature of 200 to 250°C, a target temperature of -20 to 50°C, and the solvent for the aromatic heterocyclic polymer solution is sulfolane.

2. The aromatic heterocyclic polymer in the aromatic heterocyclic polymer solution comprises one or more of the following: polyethersulfone, polyetheretherketone, and polymer A, wherein polymer A has the structure represented by formula 1. 【Chemistry 1】 Here, R １ and R ２ The manufacturing method according to claim 1, wherein is independently one or more of the following: halogen, amino group, hydroxyl group, alkyl group, alkenyl group, alkynyl group, aryl group, ether group, thioether group, carboxyl group, ester group, amide group, imide group, alkali metal sulfonic acid base, alkyl sulfonic acid ester group, alkyl phosphate ester group, amine group, and quaternary ammonium group, e is an integer from 0 to 4, and n is an integer from 1 to 300.

3. The method for producing polymer A according to claim 2, wherein polymer A comprises polyphenylene sulfone and / or polysulfone.

4. The manufacturing method according to any one of claims 1 to 3, wherein the content of the aromatic heterocyclic polymer in the aromatic heterocyclic polymer solution is 5 to 50% by mass.

5. The aromatic heterocyclic polymer solution further comprises a salt and / or a base, The manufacturing method according to any one of claims 1 to 3, wherein the content of salts and / or bases in the aromatic heterocyclic polymer solution is 5 to 15% by mass.

6. The manufacturing method according to claim 1, wherein the shearing is performed with a motor frequency of 10 to 100 Hz and a duration of 10 to 120 mins.

7. The manufacturing method according to claim 1, wherein the cooling rate is 5 to 30°C / min.

8. The process further comprises the step of mixing an aromatic heterocyclic polymer solution with a dispersant. The manufacturing method according to claim 1, wherein the dispersant comprises one or more of the following: water, liquid alcohol, liquid ether, and liquid ester.

9. The liquid alcohol comprises one or more of methanol, ethanol, and isopropanol. The liquid ether comprises one or more of methyl ether, ethyl ether, n-propyl ether, and isopropyl ether. The production method according to claim 8, wherein the liquid ester comprises one or more of ethyl formate, ethyl acetate, and butyl propionate.

10. The mass ratio of the dispersant to the aromatic heterocyclic polymer solution is 1:1 to 10. The manufacturing method according to claim 8 or claim 9, wherein the mixing temperature is 0 to 150°C.

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