Preparation method of heteroaromatic polymer powder

Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of heteroaromatic polymer powder. The preparation method of the heteroaromatic polymer powder provided by the invention comprises the following steps: synchronously cooling and shearing a heteroaromatic polymer solution to obtain the heteroaromatic polymer powder, the initial temperature of cooling is 200-250 DEG C, and the target temperature is-20-50 DEG C; the solvent of the aromatic heterocyclic polymer solution is sulfolane. According to the preparation method provided by the invention, cooling and shearing are synchronously carried out, refining is completed in the phase transformation process, the aromatic heterocyclic polymer mixture is directly prepared into the aromatic heterocyclic polymer powder, and the obtained product is uniform in morphology and narrow in particle size distribution. Moreover, according to the preparation method provided by the invention, mechanical impurities generated by mechanical friction in the crushing and crushing processes in the traditional process are avoided, pure powder can be directly obtained, and the product quality is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a method for preparing aromatic heterocyclic polymer powder. Background Art

[0002] Heteroaromatic polymers refer to polymers with heterocyclic or aromatic heterocyclic structures as the main macromolecular chain. These polymers have excellent properties such as high temperature resistance, high strength, high modulus, excellent electrical insulation, as well as radiation resistance and chemical corrosion resistance. With its excellent properties, heteroaromatic polymers have shown broad application prospects in many fields such as the electronics industry, construction industry, automobile industry, chemical industry, aerospace industry and pharmaceutical industry.

[0003] At present, the method of sequential dispersion and pulverization is usually adopted when treating the aromatic heterocyclic polymer system, specifically, the salt-containing or desalted aromatic heterocyclic polymer solution is pulled into thin strips in the dispersant by pressurization or gravity, or it is entered into the dispersant by natural particle falling through a sieve plate or pressurized injection, solidified into a spherical solid, and then processed into a flake, granular or block powder product by a crusher or pulverizer. However, the particle size of the product obtained by the above method is different, and the particle size distribution range is wide, ranging from 0.1 to 1000 μm, which leads to the disadvantages of low washing efficiency, difficult to remove residues, and low bulk density. Summary of the invention

[0004] The object of the present invention is to provide a method for preparing aromatic heterocyclic polymer powder. The aromatic heterocyclic polymer powder obtained by the preparation method provided by the present invention has uniform morphology and a narrow particle size distribution range.

[0005] In order to achieve the above object, the present invention provides the following technical solutions:

[0006] The present invention provides a method for preparing aromatic heterocyclic polymer powder, comprising the following steps:

[0007] The aromatic heterocyclic polymer solution is simultaneously cooled and sheared to obtain the aromatic heterocyclic polymer powder; the initial temperature of the cooling is 200 to 250° C., and the target temperature is -20 to 50° C.; the solvent of the aromatic heterocyclic polymer solution is sulfolane.

[0008] Preferably, the aromatic heterocyclic polymer in the aromatic heterocyclic polymer solution includes one or more of polyethersulfone, polyetheretherketone and polymer A; the polymer A has a structure shown in Formula 1:

[0009]

[0010] Wherein, R1 and R2 independently include one or more of halogen, amino, hydroxyl, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxyl, ester, amide, imide, alkali metal sulfonate, alkyl sulfonate, alkyl phosphate, amine and quaternary ammonium; e is an integer of 0 to 4; n is an integer of 1 to 300.

[0011] Preferably, the polymer A comprises polyphenylene sulfone and / or polysulfone.

[0012] Preferably, the mass percentage of the aromatic heterocyclic polymer in the aromatic heterocyclic polymer solution is 5% to 50%.

[0013] Preferably, the aromatic heterocyclic polymer solution further comprises salt and / or base;

[0014] The mass percentage of salt and / or alkali in the aromatic heterocyclic polymer solution is 5-15%.

[0015] Preferably, the shearing motor frequency is 10 to 100 Hz, and the shearing time is 10 to 120 minutes.

[0016] Preferably, the cooling rate is 5-30°C / min.

[0017] Preferably, the method further comprises mixing the aromatic heterocyclic polymer solution and a dispersant; the dispersant comprises one or more of water, liquid alcohol, liquid ether and liquid ester.

[0018] Preferably, the liquid alcohol comprises one or more of methanol, ethanol and isopropanol;

[0019] The liquid ether includes one or more of methyl ether, ethyl ether, n-propyl ether and isopropyl ether;

[0020] The liquid ester includes one or more of ethyl formate, ethyl acetate and butyl propionate.

[0021] Preferably, the mass ratio of the dispersant to the aromatic heterocyclic polymer solution is 1:1 to 10;

[0022] The mixing temperature is 0-150°C.

[0023] The present invention provides a method for preparing an aromatic heterocyclic polymer powder, comprising the following steps: cooling and shearing an aromatic heterocyclic polymer solution simultaneously to obtain the aromatic heterocyclic polymer powder; the initial temperature of the cooling is 200 to 250°C, and the target temperature is -20 to 50°C; the solvent of the aromatic heterocyclic polymer solution is sulfolane. The preparation method provided by the present invention replaces the original dispersion processes such as falling particles and drawing strips, as well as the crushing and pulverizing processes. By cooling and shearing simultaneously, as the temperature of the system gradually decreases, the viscosity of the polymer will gradually increase, and the state will change from a completely liquid state to a solid-liquid mixed state, and then to a solid state. The refinement is completed during the phase transition process, and the aromatic heterocyclic polymer mixture is directly prepared into an aromatic heterocyclic polymer powder or powder flakes. The obtained product has a uniform morphology and a narrow particle size distribution, which can avoid the problem of difficult removal of residues, and will not cause unnecessary washing waste due to large differences in particle sizes.

[0024] In addition, the preparation method provided by the present invention avoids mechanical impurities generated by mechanical friction during crushing and pulverizing in traditional processes, and can directly obtain pure powder, thereby improving the quality of the product. At the same time, the preparation method provided by the present invention can prepare powders with different particle size distribution ranges according to different application fields without the need for secondary treatment such as grinding and pulverizing. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0026] Figure 1 A comparison diagram of the process flow of the preparation method of the aromatic heterocyclic polymer powder provided by the prior art and the present invention;

[0027] Figure 2 This is a physical picture of the initial state of the salt-containing polyethersulfone solution in Example 1;

[0028] Figure 3 This is a physical picture of the intermediate state of the salt-containing polyethersulfone solution in Example 1 without adding a dispersant;

[0029] Figure 4 This is a physical picture of the final product of the salt-containing polyethersulfone solution in Example 1 without adding a dispersant;

[0030] Figure 5 This is a physical picture of the intermediate state of adding ethanol as a dispersant to the salt-containing polyethersulfone solution in Example 2;

[0031] Figure 6This is a physical picture of the final product of adding ethanol as a dispersant to the salt-containing polyethersulfone solution in Example 2;

[0032] Figure 7 This is a physical picture of the intermediate state of adding water as a dispersant to the salt-containing polyethersulfone solution in Example 3;

[0033] Figure 8 This is a physical picture of the final product obtained by adding water as a dispersant to the salt-containing polyethersulfone solution in Example 3;

[0034] Fig. 9 This is a physical picture of the initial state of the desalted polyethersulfone solution in Example 7. DETAILED DESCRIPTION

[0035] The present invention provides a method for preparing aromatic heterocyclic polymer powder, comprising the following steps:

[0036] The aromatic heterocyclic polymer solution is simultaneously cooled and sheared to obtain the aromatic heterocyclic polymer powder; the initial temperature of the cooling is 200 to 250° C., and the target temperature is -20 to 50° C.; the solvent of the aromatic heterocyclic polymer solution is sulfolane.

[0037] In the present invention, unless otherwise specified, all raw material components are commercially available products well known to those skilled in the art.

[0038] In the present invention, the aromatic heterocyclic polymer in the aromatic heterocyclic polymer solution includes one or more of polyethersulfone, polyetheretherketone and polymer A; the polymer A has a structure shown in Formula 1:

[0039]

[0040] Wherein, R1 and R2 independently may include one or more of halogen, amino, hydroxyl, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxyl, ester, amide, imide, alkali metal sulfonate, alkyl sulfonate, alkyl phosphate, amine and quaternary ammonium groups, and in specific embodiments, may be halogen, amino, hydroxyl, alkyl, alkenyl, alkynyl or aryl; e is the number of R1 groups; it may be an integer of 0 to 4, and in specific embodiments, it may be 1, 2 or 3; n may be an integer of 1 to 300, and in specific embodiments, it may be 50, 100 or 200; the polymer A may include polyphenylene sulfone and / or polysulfone.

[0041] In the present invention, the mass percentage of the aromatic heterocyclic polymer in the aromatic heterocyclic polymer solution can be 5% to 50%, and in a specific embodiment, can be 10%, 20%, 35% or 45%. In the present invention, the mass percentage of the aromatic heterocyclic polymer in the aromatic heterocyclic polymer solution is limited to the above range because in the solvent system polymerization, the polymer content will not be higher than the solvent content. If the content is too high, the fluidity is poor, which is not conducive to post-processing. At the same time, the polymer in this range is easier to handle by equipment, and solvent-free polymerization is rarely used.

[0042] In the present invention, the aromatic heterocyclic polymer solution can 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 can also include salts and / or alkalis; the salts include organic salts and / or inorganic salts; the organic salts include sodium phenolate and / or potassium phenolate; the inorganic salts are alkali metal inorganic salts; the inorganic salts include one or more of sodium bicarbonate, potassium bicarbonate, potassium carbonate and sodium carbonate; the alkalis include sodium hydroxide and / or potassium hydroxide; the mass percentage of salts and / or alkalis in the aromatic heterocyclic polymer solution is 5-15%, and in a specific embodiment, it can be 6%, 9% or 12%. The desalted aromatic heterocyclic polymer product system of the present invention refers to the remaining mixture of salts generated by the reaction and unreacted salts in the polyarylethersulfone resin mixture removed by a filtering device after polymerization, and the pure aromatic heterocyclic polymer dissolved in sulfolane.

[0043] In the present invention, the preparation method of the aromatic heterocyclic polymer product system comprises the following steps: mixing aromatic dihydroxyl, aromatic dihalogen, alkaline reagent and sulfolane, and performing polymerization reaction to obtain the aromatic heterocyclic polymer product system.

[0044] In the present invention, the aromatic dihydroxy may include one or more of hydroquinone, catechol, resorcinol, bis(hydroxyphenyl)alkane, dihydroxydiphenyl sulfone, 4,4'-biphenol and dihydroxydiphenyl ether, and in a specific embodiment, it may be 4,4-dihydroxydiphenyl sulfone; the aromatic dihalogen may include 4,4'-dichlorodiphenyl sulfone and / or 4,4'-difluorodiphenyl sulfone, and in a specific embodiment, it may be 4,4'-dichlorodiphenyl sulfone; the molar ratio of the aromatic dihydroxy monomer to the aromatic dihalogen monomer may be 1 to 1.3, and in a specific embodiment, it may be 1.02, 1.1 or 1.15; the alkaline agent may include an alkali metal inorganic salt and / or a base; the alkali metal inorganic salt may include one or more of sodium bicarbonate, potassium bicarbonate, potassium carbonate and sodium carbonate; the base may include sodium hydroxide and / or potassium hydroxide; the molar ratio of the alkaline agent to the aromatic dihydroxy monomer may be 1 to 2.5, and in a specific embodiment, it may be 1.3, 1.5, 1.8 or 2.

[0045] In the present invention, the polymerization reaction temperature is 200-240° C., and in a specific embodiment, it can be 220° C.; the polymerization reaction time is 4-9 hours, and in a specific embodiment, it can be 6 hours or 8 hours.

[0046] In the present invention, the preparation method of the desalted aromatic heterocyclic polymer product system comprises the following steps: mixing aromatic dihydroxy, aromatic dihalogen, alkaline reagent and sulfolane, and sequentially performing polymerization reaction and desalting treatment to obtain the desalted aromatic heterocyclic polymer product system.

[0047] In the present invention, the raw materials and reaction conditions of the polymerization reaction are the same as above and will not be described in detail herein.

[0048] In the present invention, the shearing motor frequency is 10-100Hz, and in a specific embodiment, it can be 40Hz, 60Hz or 80Hz; the time is 10-120min, and in a specific embodiment, it can be 30min, 50min, 80min or 100min; when the temperature of the aromatic heterocyclic polymer solution is 100-250°C, the shearing can be carried out in a nitrogen environment or an inert gas environment; when the temperature of the aromatic heterocyclic polymer solution is -20-100°C, the shearing can be carried out in a nitrogen environment, an inert gas environment or an air environment; the gas pressure of the nitrogen environment, the inert gas environment or the air environment can be normal pressure; the shearing equipment can be a kneader, a mixer, a kneading extruder or an extruder; the ratio of the volume of the aromatic heterocyclic polymer solution to the volume of the cavity of the shearing equipment can be 1:1-10, and in a specific embodiment, it can be 1:3 or 2:3. The use of the above-mentioned gas environment can prevent the polymer from discoloring due to oxidation at a temperature higher than 100°C.

[0049] In the present invention, the initial temperature of the cooling can be 200-250°C, and in a specific embodiment, it can be 220°C or 240°C; the target temperature can be -20-50°C, and in a specific embodiment, it can be -10°C, 0°C, 10°C, 20°C, 30°C, 40°C or 50°C; the cooling rate can be 5-30°C / min, and in a specific embodiment, it can be 10°C / min or 20°C / min; the cooling equipment can be an external circulation cooling equipment; the temperature of the external circulation cooling equipment can be -40-25°C, and in a specific embodiment, it can be -20°C, 0°C or 20°C.

[0050] In the present invention, the aromatic heterocyclic polymer solution and a dispersant may be mixed; 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 a specific embodiment, the dispersant may be water and / or liquid alcohol; the mass ratio of the dispersant to the aromatic heterocyclic polymer solution may be 1:1-10, and in a specific embodiment, the volume ratio of the dispersant to the aromatic heterocyclic polymer solution may be 1:2, 1:5, 1:8 or 1:1-10; the mixing temperature may be 0-150°C, and in a specific embodiment, may be 80°C, 100°C or 120°C. In the present invention, the function of the dispersant is to prevent the polymer from bonding to form large pieces that are difficult to crush.

[0051] In the present invention, the shearing may further include washing and drying in sequence; the washing may be carried out in a washing kettle; the washing agent may be water; the number of washings may be 4 to 10 times, and in a specific embodiment, may be 6 times; the time for a single washing is 1 to 3 hours, and in a specific embodiment, may be 1.5 hours; the drying may be negative pressure drying.

[0052] In the present invention, the aromatic heterocyclic polymer powder may be in granular or flaky form; the particle size of the aromatic heterocyclic polymer powder may be less than 1000 μm; when the aromatic heterocyclic polymer powder is in flaky form, the particle size may be 600-1000 μm, and in a specific embodiment, may be 700 μm, 800 μm or 900 μm; when the aromatic heterocyclic polymer powder is in granular form, the particle size may be less than 200 μm, and in a specific embodiment, may be 50 μm, 100 μm or 150 μm; the ash content of the aromatic heterocyclic polymer powder may be less than 0.3%, the bulk density may be 0.3-0.6 g / mL, and the solvent residue may be less than 0.05%.

[0053] The preparation method provided by the present invention replaces the original dispersion processes such as falling particles and drawing strips, as well as the crushing and pulverizing processes. By simultaneously performing cooling and shearing, as the system temperature gradually decreases, the viscosity of the polymer will gradually increase, and the state will change from a completely liquid state to a solid-liquid mixed state and then to a solid state. The refinement is completed during the phase transition process, and the aromatic heterocyclic polymer mixture is directly prepared into an aromatic heterocyclic polymer powder or powder flakes. The obtained product has a uniform morphology, a narrow particle size distribution, a loose surface that is easy to wash, and can avoid the problem of difficult removal of residues, and will not cause unnecessary washing waste due to large particle size differences.

[0054] In addition, the preparation method provided by the present invention avoids mechanical impurities generated by mechanical friction during crushing and pulverizing in traditional processes, and can directly obtain pure powder, thereby improving the quality of the product. At the same time, the preparation method provided by the present invention can prepare powders with different particle size distribution ranges according to different application fields without the need for secondary treatment such as grinding and pulverizing.

[0055] In order to further illustrate the present invention, the preparation method of the aromatic heterocyclic polymer powder provided by the present invention is described in detail below in conjunction with the accompanying drawings and examples, but they should not be construed as limiting the scope of protection of the present invention.

[0056] Figure 1 This is a comparison chart of the process flow of the preparation method of aromatic heterocyclic polymer powder provided by the prior art and the present invention. Figure 1 It can be seen that the present invention replaces the dispersion device, the crushing device and the pulverizing device with a high shearing device, simplifies the process steps, replaces three with one, avoids the pollution caused by the process, and saves costs.

[0057] In the embodiments of the present invention, unless otherwise specified, the kneading machine speed is set to 45 Hz, and the cooling rate is determined by the cooling circulation device, and the cooling rate is set to 10° C. / min.

[0058] Comparative Example 1

[0059] 2552.7581g (10.02mol) of 4,4-dihydroxydiphenyl sulfone, 2871.600g (10.00mol) of 4,4'-dichlorodiphenyl sulfone, 1621.647g (15.3mol) of sodium carbonate and 10836.709g (90.2mol) of cyclopentane sulfone were added into a 30000ml polymerization kettle, replaced with nitrogen three times, heated to 235°C under nitrogen protection, reacted for 8h, and obtained a salt-containing polyethersulfone product system with a solid content of 30%. The product system was dispersed into pure water in the form of strands, and then mechanically crushed and pulverized in sequence, washed with pure water 6 times, and dried under negative pressure to obtain a powder.

[0060] Example 1

[0061] A salt-containing polyethersulfone product system was obtained according to the preparation method of Comparative Example 1, and a kneader with a cavity volume of 5 L and an external cooling circulation device set at 5°C were started. The air was replaced with nitrogen three times to maintain a nitrogen environment. 3L of a salt-containing polyethersulfone product system with a solid content of 30% was added into the kneader cavity. When the temperature dropped to 35°C, the material in the cavity was solidified and crushed into powder. After 6 times of pure water washing and negative pressure drying, a pure powder was obtained.

[0062] Example 2

[0063] A salt-containing polyethersulfone product system was obtained according to the preparation method of Comparative Example 1, a kneader with a cavity volume of 5L and an external cooling circulation device set at 5°C were started, the air was replaced with nitrogen 3 times, and a nitrogen environment was maintained. 3L of a salt-containing polyethersulfone product system with a solid content of 30% was added into the kneader cavity. When the temperature dropped to 120°C, ethanol was added thereto through a pipeline. 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 was solidified and crushed into powder. After 6 times of pure water washing and negative pressure drying, a pure powder was obtained.

[0064] Example 3

[0065] According to the preparation method of comparative example 1, a salt-containing polyethersulfone product system was prepared, a kneading machine with a cavity volume of 5L and an external cooling circulation device set at 5°C were started, the air was replaced with nitrogen 3 times, and a nitrogen environment was maintained. 3L of a salt-containing polyethersulfone product system with a solid content of 30% was added to the kneading machine cavity. When the temperature dropped to 120°C, water was added through a pipeline. 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 was solidified and crushed into powder. After 6 times of pure water washing and negative pressure drying, a pure powder was obtained.

[0066] Comparative Example 2

[0067] 1899.3420g (10.02mol) of 4,4'-biphenyldiphenol, 2871.600g (10.00mol) of 4,4'-dichlorodiphenyl sulfone, 1621.647g (15.3mol) of sodium carbonate and 9428.8647g (78.46mol) of cyclopentane sulfone were added into a 30000ml polymerization kettle, replaced with nitrogen three times, heated to 230°C under nitrogen protection, reacted for 8h, and obtained a salt-containing polyphenylene sulfone product system with a solid content of 30%. The product system was dispersed into pure water in the form of strands, and then mechanically crushed and pulverized in sequence, washed with pure water 6 times, and dried under negative pressure to obtain a powder.

[0068] Example 4

[0069] A salt-containing polyphenylene sulfone product system was prepared according to the preparation method of Comparative Example 2, and a kneader with a cavity volume of 5L and an external cooling circulation device set at 5°C were started. The air was replaced with nitrogen 3 times to maintain a nitrogen environment. 3L of a salt-containing polyphenylene sulfone product system with a solid content of 30% was added to the kneader cavity. When the temperature dropped to 40°C, the material in the cavity was solidified and crushed into powder. After 6 times of pure water washing and negative pressure drying, a pure powder was obtained.

[0070] Example 5

[0071] A salt-containing polyphenylene sulfone product system was prepared according to the preparation method of Comparative Example 2, a kneader with a cavity volume of 5L and an external cooling circulation device set at -5°C were started, the air was replaced with nitrogen 3 times, and a nitrogen environment was maintained. 3L of a salt-containing polyphenylene sulfone product system with a solid content of 30% was added into the kneader cavity. When the temperature dropped to 120°C, ethanol was added thereto through a pipeline. 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 was solidified and crushed into powder. After 6 times of pure water washing and negative pressure drying, a pure powder was obtained.

[0072] Example 6

[0073] A salt-containing polyphenylene sulfone product system was prepared according to the preparation method of Comparative Example 2, a kneader with a cavity volume of 5L and an external cooling circulation device set at 5°C were started, the air was replaced with nitrogen 3 times, and a nitrogen environment was maintained. 3L of a salt-containing polyphenylene sulfone product system with a solid content of 30% was added to the kneader cavity. When the temperature dropped to 120°C, water was added thereto through a pipeline. 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 was solidified and crushed into powder. After 6 times of pure water washing and negative pressure drying, a pure powder was obtained.

[0074] Comparative Example 3

[0075] 2552.7581g (10.02mol) of 4,4-dihydroxydiphenyl sulfone, 2871.600g (10.00mol) of 4,4'-dichlorodiphenyl sulfone, 1621.647g (15.3mol) of sodium carbonate and 10836.709g (90.2mol) of cyclopentane sulfone were added into a 30000ml polymerization kettle, replaced with nitrogen three times, heated to 235°C under nitrogen protection, reacted for 8h to obtain a salt-containing polyethersulfone product system, and the salt was removed by a pressurized desalting filter device to obtain a desalted polyethersulfone product system with a solid content of 35%, which was dispersed into pure water in the form of strands, and then mechanically crushed and mechanically pulverized in sequence, washed with pure water 6 times, and dried under negative pressure to obtain a powder.

[0076] Example 7

[0077] According to the preparation method of Comparative Example 3, a desalted polyethersulfone product system with a solid content of 35% is prepared. A kneader with a cavity volume of 5L and an external cooling circulation device set to 5°C are started. The air is replaced with nitrogen 3 times to maintain a nitrogen environment. 3L of the desalted polyethersulfone product system with a solid content of 35% is added into the kneader cavity. When the temperature drops to 35°C, the material in the cavity will solidify and be crushed into powder. After 6 times of pure water washing and negative pressure drying, a pure powder is obtained.

[0078] Example 8

[0079] A desalted polyethersulfone product system with a solid content of 35% was prepared according to the preparation method of Comparative Example 3. A kneader with a cavity volume of 5 L and an external cooling circulation device set at -5°C were started, the air was replaced with nitrogen for 3 times, and a nitrogen environment was maintained. 3L of the desalted polyethersulfone product system with a solid content of 35% was added into the kneader cavity. When the temperature dropped to 120°C, ethanol was added thereto through a pipeline. 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 was solidified and crushed into powder. After 6 times of pure water washing and negative pressure drying, a pure powder was obtained.

[0080] Example 9

[0081] A desalted polyethersulfone product system with a solid content of 35% was prepared according to the preparation method of Comparative Example 3. A kneader with a cavity volume of 5 L and an external cooling circulation device set at 5°C were started. The air was replaced with nitrogen three times to maintain a nitrogen environment. 3L of the desalted polyethersulfone product system with a solid content of 35% was added into the kneader cavity. When the temperature dropped to 120°C, water was added through a pipeline. 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 was solidified and crushed into powder. After 6 times of pure water washing and negative pressure drying, a pure powder was obtained.

[0082] Comparative Example 4

[0083] 1899.3420g (10.02mol) of 4,4'-biphenyldiphenol, 2871.600g (10.00mol) of 4,4'-dichlorodiphenyl sulfone, 1621.647g (15.3mol) of sodium carbonate and 9428.8647g (78.46mol) of cyclopentane sulfone were added into a 30000ml polymerization kettle, replaced with nitrogen three times, heated to 230°C under nitrogen protection, reacted for 8h, and obtained a salt-containing polyphenylene sulfone product system. The salt was removed by a pressurized desalting filter device to obtain a desalted polyphenylene sulfone product system with a solid content of 35%. The system was dispersed into pure water in the form of strands, and then mechanically crushed and pulverized in sequence, washed with pure water 6 times, and dried under negative pressure to obtain a powder.

[0084] Example 10

[0085] A desalted polyphenylene sulfone product system was prepared according to the preparation method of Comparative Example 4, a kneader with a cavity volume of 5 L and an external cooling circulation device set at 5° C. was started, the air was replaced with nitrogen 3 times, and a nitrogen environment was maintained. 3 L of desalted polyphenylene sulfone resin with a solid content of 35% was added into the kneader cavity. When the temperature dropped to 35° C., the material in the cavity was solidified and crushed into powder. After 6 times of pure water washing and negative pressure drying treatment, a pure powder was obtained, and its solvent residue, ash content, particle size distribution, and loose density data were tested.

[0086] Embodiment 11

[0087] A desalted polyphenylene sulfone product system was prepared according to the preparation method of Comparative Example 4, a kneader with a cavity volume of 5L and an external cooling circulation device set at 5°C were started, the air was replaced with nitrogen 3 times, and a nitrogen environment was maintained. 3L of desalted polyphenylene sulfone resin with a solid content of 35% was added into the kneader cavity. When the temperature dropped to 120°C, ethanol was added thereto through a pipeline. 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 was solidified and crushed into powder. After 6 times of pure water washing and negative pressure drying treatment, a pure powder was obtained, and its solvent residue, ash content, particle size distribution, and loose density data were tested.

[0088] Example 12

[0089] A desalted polyphenylene sulfone product system was prepared according to the preparation method of Comparative Example 4, a kneader with a cavity volume of 5L and an external cooling circulation device set at 5°C were started, the air was replaced with nitrogen 3 times, and a nitrogen environment was maintained. 3L of desalted polyphenylene sulfone resin with a solid content of 35% was added into the kneader cavity. When the temperature dropped to 120°C, water was added thereto through a pipeline. 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 was solidified and crushed into powder. After 6 times of pure water washing and negative pressure drying treatment, a pure powder was obtained, and its solvent residue, ash content, particle size distribution, and loose density data were tested.

[0090] Comparative Example 5

[0091] The polysulfone resin powder with a particle size greater than 300 μm was completely dissolved in cyclopentane sulfone at 160° C. to prepare 3 L of a 30% solid content salt-free polysulfone resin solution, which was dispersed into pure water in the form of strands, and then mechanically crushed and pulverized in sequence, washed with pure water 6 times, and dried under negative pressure to obtain a powder.

[0092] Example 13

[0093] Start a kneading machine with a cavity volume of 5L and an external cooling circulation device set at 5℃, replace the air with nitrogen for 3 times, maintain a nitrogen environment, add 3L of salt-free polysulfone resin solution with a solid content of 30%, and add it into the kneading machine cavity. When the temperature drops to 35℃, the material in the cavity will solidify and be crushed into powder. After 6 times of pure water washing and negative pressure drying, pure powder can be obtained.

[0094] Embodiment 14

[0095] Start a kneading machine with a cavity volume of 5L and an external cooling circulation device set at 5℃, replace the air with nitrogen for 3 times, maintain a nitrogen environment, add 3L of salt-free polysulfone resin solution with a solid content of 30% into the kneading machine cavity, and when the temperature drops to 120℃, add ethanol through a pipe. The mass ratio of ethanol to salt-free polyethersulfone resin solution is 1:10. When the temperature drops to 30℃, the material in the cavity will solidify and be crushed into powder. After 6 times of pure water washing and negative pressure drying, pure powder is obtained.

[0096] Embodiment 15

[0097] Start a kneading machine with a cavity volume of 5L and an external cooling circulation device set at 5℃, replace the air with nitrogen for 3 times, maintain a nitrogen environment, add 3L of salt-free polysulfone resin solution with a solid content of 30% into the kneading machine cavity, and when the temperature drops to 120℃, add water through a pipe. The mass ratio of water to salt-free polyethersulfone resin solution is 1:2. When the temperature drops to 45℃, the material in the cavity will solidify and be crushed into powder. After 6 times of pure water washing and negative pressure drying, pure powder is obtained.

[0098] In the embodiments of the present invention, the appearance of the aromatic heterocyclic polymer in the dissolved state in the sulfolane system is the same, and the state change in the kneader is also the same, so the same treatment method can be used to obtain the same effect. Figure 2 This is a physical picture of the initial state of the salt-containing polyethersulfone solution in Example 1, and Examples 2 to 6 are consistent with it; Figure 3 This is a physical picture of the intermediate state of the salt-containing polyethersulfone solution in Example 1 without adding a dispersant, and Examples 4, 7, 10 and 13 are consistent with it; Figure 4 This is a physical picture of the final product of the salt-containing polyethersulfone solution in Example 1 without adding a dispersant, and Examples 4, 7, 10 and 13 are consistent with it; Figure 5 This is a physical picture of the intermediate state of adding ethanol as a dispersant to the salt-containing polyethersulfone solution in Example 2, and Examples 5, 8, 11 and 14 are consistent with it; Figure 6 This is a physical picture of the final product of adding ethanol as a dispersant to the salt-containing polyethersulfone solution in Example 2, and Examples 5, 8, 11 and 14 are consistent with it; Figure 7 This is a physical picture of the intermediate state of adding water as a dispersant to the salt-containing polyethersulfone solution in Example 3, and Examples 6, 9, 12 and 15 are consistent with it; Figure 8 This is a physical picture of the final product of adding water as a dispersant to the salt-containing polyethersulfone solution in Example 3, and Examples 6, 9, 12 and 15 are consistent with it; Fig. 9 This is a physical picture of the initial state of the desalted polyethersulfone solution in Example 7, which is consistent with Examples 8 to 15.

[0099] Depend on Figures 2 to 6It can be seen that in the solution provided by the present invention, the aromatic heterocyclic polymer resin containing salt and the desalting system have different colors, but they appear in the same state in the kneading machine. After kneading for a certain period of time, no dispersant is added and the color appears. Figure 3 state; adding 10% ethanol will gradually form granular polyethersulfone powder as the kneading time increases; adding 50% water will gradually form blocky polyethersulfone powder as the kneading time increases, and finally form aromatic heterocyclic polymer powder or powder flakes.

[0100] Test Case

[0101] The powder products obtained in Comparative Examples 1 to 5 and Examples 1 to 15 were tested for powderization time, ash content, bulk density, solvent residue and particle size distribution data. The ash residue was determined by a thermal gravimetric analyzer (TGA) produced by TG Company of the United States, the bulk density was determined by a BT-100 universal powder bulk density tester, the solvent residue was determined by a gas chromatograph produced by Shimadzu Corporation of Japan, and the particle size distribution was determined by an OMEC laser particle size analyzer. The test results are shown in Table 1.

[0102] Table 1 Performance data of powder products obtained in Comparative Examples 1 to 5 and Examples 1 to 15

[0103]

[0104]

[0105] As shown in Table 1, whether or not a dispersant is added in the solution provided by the present invention, a powder product of excellent quality can be prepared; the particle size of the product becomes smaller with the addition of the ethanol additive, and changes from granular to thin block with the addition of water. In short, in the solution provided by the present invention, no matter what state, the polymer can be directly prepared into a powder product of the desired state without the need for dispersion shaping, crushing and pulverization processes, and the particle size distribution is narrow.

[0106] It can be seen from the above embodiments that the present invention adopts equipment with shearing function and circulating cooling equipment, utilizes the properties of aromatic heterocyclic polymers in the cyclopentane sulfone system, and adjusts parameters such as the solid content of heterocyclic polymers, the amount of dispersant used and the cooling temperature to achieve innovation in the processing technology of aromatic heterocyclic polymers and replace part of the traditional process. The powder products prepared by the invention do not need special treatment and can meet the market application needs, thereby greatly improving the production efficiency, reducing costs and improving quality.

[0107] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for preparing aromatic heterocyclic polymer powder, characterized in that: The following steps are involved: The aromatic heterocyclic polymer solution is simultaneously cooled and sheared to obtain the aromatic heterocyclic polymer powder; the initial temperature of the cooling is 200 to 250° C., and the target temperature is -20 to 50° C.; the solvent of the aromatic heterocyclic polymer solution is sulfolane.

2. The preparation method according to claim 1, characterized in that: The aromatic heterocyclic polymer in the aromatic heterocyclic polymer solution includes one or more of polyethersulfone, polyetheretherketone and polymer A; the polymer A has a structure shown in Formula 1: Wherein, R1 and R2 independently include one or more of halogen, amino, hydroxyl, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxyl, ester, amide, imide, alkali metal sulfonate, alkyl sulfonate, alkyl phosphate, amine and quaternary ammonium; e is an integer of 0 to 4; n is an integer of 1 to 300.

3. The preparation method according to claim 2, characterized in that: The polymer A includes polyphenylene sulfone and / or polysulfone.

4. The preparation method according to any one of claims 1 to 3, characterized in that: The mass percentage of the aromatic heterocyclic polymer in the aromatic heterocyclic polymer solution is 5% to 50%.

5. The preparation method according to any one of claims 1 to 3, characterized in that: The aromatic heterocyclic polymer solution also includes salt and / or base; The mass percentage of salt and / or alkali in the aromatic heterocyclic polymer solution is 5-15%.

6. The preparation method according to claim 1, characterized in that: The shearing motor frequency is 10-100 Hz, and the shearing time is 10-120 minutes.

7. The preparation method according to claim 1, characterized in that: The cooling rate is 5-30°C / min.

8. The preparation method according to claim 1, characterized in that: The method further comprises mixing the aromatic heterocyclic polymer solution and a dispersant; the dispersant comprises one or more of water, liquid alcohol, liquid ether and liquid ester.

9. The preparation method according to claim 8, characterized in that: The liquid alcohol includes one or more of methanol, ethanol and isopropanol; The liquid ether includes one or more of methyl ether, ethyl ether, n-propyl ether and isopropyl ether; The liquid ester includes one or more of ethyl formate, ethyl acetate and butyl propionate.

10. The preparation method according to claim 8 or 9, characterized in that: The mass ratio of the dispersant to the aromatic heterocyclic polymer solution is 1:1 to 10; The mixing temperature is 0-150°C.

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