Spherical sodium carbonate, preparation method thereof and application of spherical sodium carbonate in high-efficiency synthesis of polyether-ether-ketone

Abstract

The invention discloses spherical sodium carbonate, a preparation method thereof and application of the spherical sodium carbonate in high-efficiency synthesis of polyether-ether-ketone. The particle size distribution of the spherical sodium carbonate is as follows: D50 is 100-250 [mu] m, and D90 is 250-400 [mu] m; the specific surface area of the spherical sodium carbonate is 0.5-3.5 m < 2 > / g; the circularity of the spherical sodium carbonate is greater than 0.8. According to the invention, the sodium carbonate with high circularity is prepared; according to the method, alkyl sulfate, alkyl phosphate, alkyl sulfonate, alkyl naphthalene sulfonate or alkyl benzene sulfonate with the carbon chain length of C1-C18 is used as an anionic surfactant, and the microstructure of sodium carbonate is regulated and controlled. When the sodium carbonate with high circularity prepared by the method is used for synthesizing the polyether-ether-ketone resin, the polymerization reaction time can be shortened, for example, the polymerization reaction time can be shortened by about 20%.

Description

Technical Field

[0001] The present invention relates to spherical sodium carbonate, a preparation method thereof, and an application thereof in the high-efficiency synthesis of polyether ether ketone, belonging to the technical field of polymer material synthesis. Background Art

[0002] Polyether ether ketone (PEEK) is a linear aromatic polymer material, which is obtained by condensation reaction of 4,4-difluorobenzophenone and hydroquinone in the presence of an alkali metal carbonate using diphenyl sulfone as a solvent. It belongs to the variety with the most excellent performance among polyaryletherketone special engineering plastics. Generally, it can be directly used as a high-temperature resistant structural material and an electrical insulating material, and has been widely used in the fields of aerospace, electronic information, petrochemical industry, medical and health, household appliances, automobile manufacturing, etc.

[0003] Sodium carbonate is a very important raw material in the synthesis process of polyether ether ketone. All along, the R & D focus of technicians in the industry has been more on process conditions such as the usage amount of sodium carbonate, the particle size of sodium carbonate, and the salt-forming temperature of sodium carbonate. There has been no relevant report on the influence of the microscopic morphology of sodium carbonate on the synthesis process and product performance of polyether ether ketone.

[0004] Sodium carbonate belongs to the monoclinic system under normal temperature conditions. Under certain experimental control conditions, technicians have developed various morphologies of sodium carbonate, including cubic, needle-shaped, rod-shaped, sheet-shaped, etc. For sodium carbonate with different morphologies, its industrial application fields are also different. Spherical sodium carbonate has a large specific surface area, uniform particle size distribution, good dispersion performance, and high solubility. These characteristics make it possible for spherical sodium carbonate to have excellent performance in the field of polyether ether ketone synthesis.

[0005] At present, the development and utilization of the microscopic morphology of sodium carbonate are still relatively backward. The existing technology for the research on the morphology regulation of sodium carbonate generally obtains the corresponding shape of sodium carbonate, and basically does not mention its function and available value. There is no report on the ability to significantly increase the specific surface area while regulating the appearance morphology of sodium carbonate. The existing methods for regulating the morphology of sodium carbonate are mainly divided into physical methods and chemical methods. The physical method mainly uses mechanical grinding means, but obviously, the obtained microscopic morphology will not be particularly uniform and the sphericity is poor. The chemical method generally uses crystal form control agents to regulate the nucleation and crystallization of sodium carbonate and control its crystal form and morphology. These crystal form control agents are mainly divided into inorganic salts, acids, alcohols, amino acids, etc. The existing technology has the disadvantages of large particle size of sodium carbonate products, low sphericity, non-uniform morphology, or relatively complicated synthesis steps and a large variety of reagents used. Therefore, it is extremely important to find a suitable morphology control agent for the preparation of spherical sodium carbonate. Summary of the Invention

[0006] To solve the above technical problems, the present invention provides the following technical solutions:

[0007] A spherical sodium carbonate, the particle size distribution of the spherical sodium carbonate includes: D50 is 100 - 250 μm (for example, 150 μm, 200 μm), and D90 is 250 - 400 μm (for example, 300 μm, 350 μm).

[0008] According to an embodiment of the present invention, the specific surface area of the spherical sodium carbonate is 0.5 - 3.5 m 2 / g, preferably 2 - 3.5 m 2 / g (for example, 2.5 m 2 / g, 3 m 2 / g).

[0009] According to an embodiment of the present invention, the roundness of the spherical sodium carbonate is greater than 0.8 (for example, 0.85, 0.9, 0.95); further, the roundness of the spherical sodium carbonate of the present invention is greater than 0.9 (for example, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99).

[0010] The present invention also provides a method for preparing the above spherical sodium carbonate, the preparation method includes: mixing a sodium carbonate solution and a surfactant solution to obtain a mixed solution, cooling the mixed solution at a cooling rate of 0.2 - 0.5 °C / min to 5 - 8 °C, continuously reacting at 5 - 8 °C for 2 - 3 hours to obtain a solid-liquid mixture, filtering to obtain a solid substance, and performing wet grinding to obtain the spherical sodium carbonate.

[0011] According to an embodiment of the present invention, the sodium carbonate solution is an aqueous solution of sodium carbonate, and its concentration is 4.0 - 4.5 mol / L. Preferably, the aqueous solution of sodium carbonate can be prepared by a method known in the art, for example: adding sodium carbonate powder to deionized water for dissolution, and stirring (the stirring speed is, for example, 60 r / min, and the stirring time is, for example, 30 minutes) under a temperature condition of 30 - 35 °C; further, the sodium carbonate powder is a commercial sodium carbonate with a purity > 99.95%.

[0012] According to an embodiment of the present invention, the surfactant solution comprises an anionic surfactant and water, wherein the concentration of the anionic surfactant is 0.005 - 0.01 mol / L. Preferably, the pH of the surfactant solution is greater than 7, preferably 7.2 - 11.0. Preferably, the surfactant solution can be prepared by a method known in the art. For example, the anionic surfactant is added to deionized water for dissolution, and under the temperature condition of 30 - 35 °C, stirring is carried out (the stirring speed is, for example, 60 r / min, and the stirring time is, for example, 30 minutes), and an alkaline regulator (such as ammonia water) is added to obtain the surfactant solution.

[0013] According to an embodiment of the present invention, the anionic surfactant is selected from at least one of alkyl sulfates, alkyl phosphates, alkyl sulfonates, alkyl naphthalene sulfonates, or alkyl benzene sulfonates having a carbon chain length of C1 - C18.

[0014] Preferably, the anionic surfactant is selected from at least one of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium diisopropyl naphthalene sulfonate, sodium dibutyl naphthalene sulfonate, sodium dibutyl sulfosuccinate, sodium dihexyl sulfosuccinate, and secondary alcohol sodium sulfate.

[0015] The inventors found that when the anionic surfactant is added to the sodium carbonate solution, the hydrophobic alkyl chain segments on the anionic surfactant change the surface energy of the sodium carbonate crystals in all directions. When sodium carbonate crystallizes at low temperature, it promotes the isotropy of the crystals, reduces the anisotropy of the crystals, inhibits the growth of the crystals in the linear direction, reduces the aspect ratio of the sodium carbonate particles, and gradually obtains the spherical sodium carbonate of the present invention.

[0016] According to an embodiment of the present invention, the specific process of mixing the sodium carbonate solution and the surfactant solution to obtain a mixed solution is as follows: Under the temperature condition of 30 - 35 °C, under the conditions of low-frequency ultrasonic dispersion and stirring, the surfactant solution is added dropwise to the sodium carbonate solution until a trace amount of flocculent precipitate appears, then the addition is stopped and stirring is continued (for example, stirring for 60 minutes) to obtain the mixed solution. Preferably, the stirring condition is that the stirring speed is 10 - 100 r / min, for example, 60 r / min. Preferably, the dropping refers to the dropping speed of the surfactant solution being 10 - 20 drops per minute.

[0017] According to an embodiment of the present invention, after filtering the solid-liquid mixture to obtain a solid substance, the solid substance also needs to be washed, and a method known in the art can be selected for washing. For example, it is washed 8 - 10 times with an alcohol solvent (such as at least one of methanol, ethanol, butanol, ethylene glycol, and propanol).

[0018] According to an embodiment of the present invention, the wet grinding specifically refers to: mixing a solid substance and an alcohol solvent (such as propanol) and then performing wet grinding in a ball mill. Preferably, the material of the grinding balls in the ball mill can be selected from at least one of stainless steel, hard steel, agate, and zirconia. Preferably, the vibration frequency of the ball mill is 100 - 500 r / min, preferably 200 - 300 r / min. Using the wet grinding of the present invention can keep the spherical shape of sodium carbonate in the solid substance from being damaged.

[0019] According to an embodiment of the present invention, after the wet grinding, spherical sodium carbonate can be obtained by removing the alcohol solvent. Preferably, the removal of the alcohol solvent can be carried out by a method known in the art, for example, first filtering and then drying (for example, drying at 80 °C for 8 hours).

[0020] The present invention also provides the use of the above spherical sodium carbonate in the preparation of polyetheretherketone resin.

[0021] The present invention also provides a polyetheretherketone resin, which is prepared by using the above spherical sodium carbonate.

[0022] According to an embodiment of the present invention, the polydispersity index PDI of the polyetheretherketone resin is 3.0 - 5.0, preferably 3 - 4, for example, 2.1, 2.5, 3, 3.1, 3.2, 3.3, 3.4.

[0023] According to an embodiment of the present invention, the mechanical properties of the polyetheretherketone resin are as follows: the impact strength is 8 - 10 KJ / m 2 , for example, 8 KJ / m 2 , 9 KJ / m 2 , 10 KJ / m 2 ; the tensile strength is not less than 90 MPa, for example, 95 MPa, 96 MPa, 97 MPa, 98 MPa; the elongation at break is more than 70%, for example, 75%, 80%, 85%, 90%; the flexural strength is not less than 140 MPa, for example, 140 MPa, 145 MPa, 146 MPa, 150 MPa; the flexural modulus is not less than 3400 MPa, for example, 3410 MPa, 3420 MPa, 3430 MPa, 3440 MPa, 3450 MPa.

[0024] According to an embodiment of the present invention, the polyetheretherketone resin has thermal stability, for example, it is thermally stable below 590 °C, or for example, it is stable in the range of 580 - 590 °C.

[0025] According to an embodiment of the present invention, in the chromaticity of the polyether ether ketone resin, the L value is greater than 70, for example, 70.5, 71, 72, 73, 74, 75; the a value is 1 to 4, for example, 2.50, 2.59, 2.70, 2.52, 2.62, 2.48; the b value is not greater than 10, preferably 4 to 9, for example, 5, 6, 7.

[0026] The present invention also provides a method for preparing the above polyether ether ketone resin, and the method includes the following steps:

[0027] (1) Under the protection of an inert gas, the above spherical sodium carbonate, bisphenol, and organic dihalide are mixed to obtain a mixture;

[0028] (2) The mixture obtained in step (1) is heated to a molten state, and then heated to a polymerization reaction temperature for a polymerization reaction;

[0029] (3) After adding an organic halide to step (2) for end-capping treatment, a reaction product is obtained;

[0030] (4) After the reaction product obtained in step (3) is cooled, crushed, purified, and dried, the polyether ether ketone resin is obtained.

[0031] According to an embodiment of the present invention, in step (1), the spherical sodium carbonate has the meaning as described above.

[0032] According to an embodiment of the present invention, step (1) is carried out under the protection of an inert gas (such as nitrogen).

[0033] According to an embodiment of the present invention, in step (1), potassium carbonate is also optionally added. Preferably, the particle size distribution of the potassium carbonate is as follows: 35 μm ≤ D50 ≤ 350 μm, and 100 μm ≤ D90 ≤ 500 μm.

[0034] According to an embodiment of the present invention, in step (1), when spherical sodium carbonate and potassium carbonate are added simultaneously, the molar ratio of spherical sodium carbonate to potassium carbonate is 10 - 100:0.1 - 10, for example, 10 - 100:1, and for another example, 1 - 5:0.01 - 0.5, and an example is 4.8:0.16.

[0035] According to an embodiment of the present invention, the molar ratio of the spherical sodium carbonate to the bisphenol is (1.003 - 1.3):1, for example, 1.2:1.

[0036] According to an embodiment of the present invention, the molar ratio of the organic dihalide to the bisphenol is (1.01 - 1.025):1, for example, 1.02:1.

[0037] According to an embodiment of the present invention, the organic dihalide is selected from at least one or a mixture of two or more of 4,4'-difluorobenzophenone, 2,4'-difluorobenzophenone, 4-chloro-4'-fluorobenzophenone, 4,4'-dichlorobenzophenone, 1,4-bis(4'-fluorobenzoyl)benzene, and preferably 4,4'-difluorobenzophenone.

[0038] According to an embodiment of the present invention, the bisphenol is selected from at least one or a mixture of two or more of hydroquinone, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl ether, 1,4-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and preferably hydroquinone.

[0039] According to an embodiment of the present invention, the organic halide is selected from monofluoro-substituted aromatic halides. Preferably, the aromatic halide includes at least 2 aryl groups, wherein the substituent on one aryl group includes -F, and the substituent on the other aryl group is selected from at least one of a hydrogen atom, -SO3, -NO2, -NH3, -Cl, -Br, -I; for example, selected from 4-fluorobenzophenone, 4-fluoro-4-bromobenzophenone, 4-fluoro-4-iodobenzophenone, 4-fluoro-4-chlorobenzophenone, 4-fluoro-4-nitrobenzophenone, 2-chloro-4-fluorobenzophenone, 4-fluoro-4-chlorobenzophenone, and preferably 4-fluorobenzophenone.

[0040] According to an embodiment of the present invention, in step (2), heating to the molten state means that all reactants are in a fluid state; exemplarily, the temperature when heating to the molten state is not less than 150 °C, for example, 180 °C.

[0041] According to an embodiment of the present invention, in step (2), after heating to the molten state, keep the temperature constant for a period of time. For example, when the temperature when heating to the molten state is 180 °C, maintain a constant temperature of 180 °C for 1 hour.

[0042] According to an embodiment of the present invention, in step (2), the polymerization reaction temperature is 250 - 320 °C (for example, 250 °C, 300 °C, 310 °C).

[0043] According to an embodiment of the present invention, in step (2), the polymerization reaction time is not higher than 250 minutes, for example, 230 minutes, 240 minutes.

[0044] According to an embodiment of the present invention, in step (3), the end-capping treatment is carried out in the presence of an end-capping agent. The end-capping agent can be a compound known in the art that can be used as an end-capping agent in the preparation process of polyether ether ketone, such as unsubstituted or substituted benzophenone, wherein the substituent of the substituted benzophenone can be a halogen (such as fluorine or chlorine), C 1-6 alkyl (such as methyl, ethyl, propyl or isopropyl), C 1-6Alkoxy groups (such as methoxy, ethoxy, propoxy, isopropoxy), and examples thereof can be 4-fluorobenzophenone, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 2,4'-difluorobenzophenone, 4-fluoro-4'-methoxybenzophenone.

[0045] According to an embodiment of the present invention, in step (3), the conditions for the capping treatment include: the temperature is 295 - 320 °C; the time is 15 - 45 min.

[0046] According to an embodiment of the present invention, in step (4), the cooling can be carried out by a method known in the art, for example, placing the reaction product on a metal plate (such as a stainless steel plate) for cooling.

[0047] According to an embodiment of the present invention, in step (4), the cooled reaction product is ground into powder particles. Preferably, the size of the powder particles is less than 1.3 mm and greater than 0.22 mm.

[0048] According to an embodiment of the present invention, in step (4), the purification includes first washing the powder particles with an organic solvent and then performing multiple water washes.

[0049] Preferably, the washing of the powder particles with the organic solvent specifically includes: mixing the powder particles with the organic solvent, removing impurities in the powder particles (such as the solvent added in step (1)), and then removing the organic solvent. Preferably, a suitable separation device is used to remove the organic solvent, such as using a Soxhlet extractor for separation. Further, during washing, the organic solvent is selected from organic solvents miscible with water, such as acetone.

[0050] Preferably, the water wash specifically includes: performing a first water wash on the powder particles with ultrapure water and / or deionized water to remove the organic solvent, and then rinsing with deionized water or pure water under heating conditions. The heating temperature is 60 - 80 °C.

[0051] Preferably, the number of times of the water wash is not specifically limited, as long as the conductivity of the filtered water after rinsing is less than 10 μS / cm.

[0052] According to an embodiment of the present invention, in step (4), the drying can be carried out by a method known in the art, as long as the washed polyetheretherketone resin can be dried.

[0053] The present invention also provides the application of the above polyetheretherketone resin in the fields of aerospace, medical treatment, electronic appliances, automobile manufacturing, petrochemical industry, etc., such as the application in film products.

[0054] The beneficial effects produced by the present invention include:

[0055] The present invention prepares a sodium carbonate with high roundness; a method for regulating the microscopic morphology of sodium carbonate by using an alkyl sulfate, alkyl phosphate, alkyl sulfonate, alkyl naphthalene sulfonate or alkyl benzene sulfonate with a carbon chain length of C1-C18 as an anionic surfactant.

[0056] Using the sodium carbonate with high roundness prepared by the present invention to synthesize a polyether ether ketone resin can shorten the polymerization reaction time. For example, the polymerization reaction time can be shortened by about 20%. Description of the Drawings

[0057] Figure 1 It is a scanning electron microscope (SEM) image of the spherical sodium carbonate prepared in Example 1 of the present invention.

[0058] Figure 2 It is a scanning electron microscope (SEM) image of the spherical sodium carbonate prepared in Example 2 of the present invention.

[0059] Figure 3 It is an infrared transmission spectrum of the polyether ether ketone material prepared in Application Example 1 of the present invention. Detailed Description of the Invention

[0060] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are only illustrative of and explanatory of the present invention, and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0061] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0062] Example 1

[0063] 1. Add 404.0 g of sodium carbonate powder to 1 L of deionized water for dissolution. Under the temperature condition of 30-35 °C and the stirring speed of 60 r / min, a sodium carbonate solution with a concentration of 4.0 mol / L is obtained, and stir at a constant speed for 30 minutes;

[0064] 2. Add 1.63 g of anionic surfactant sodium dodecyl sulfonate to 1 L of deionized water for dissolution. Under the temperature condition of 30-35 °C and the stirring speed of 60 r / min, a sodium dodecyl sulfonate solution with a concentration of 0.006 mol / L is obtained. Use ammonia water to adjust the pH value of the solution to 7.2-11.0, and stir at a constant speed for 30 minutes;

[0065] 3. Under the condition of low-frequency ultrasonic dispersion, at a temperature of 30 - 35 °C and a stirring speed of 60 r / min, slowly add the sodium dodecyl sulfonate solution to the sodium carbonate solution until a trace amount of flocculent precipitate appears, and stir at a constant speed for 60 minutes to obtain a mixed solution;

[0066] 4. Slowly cool the mixed solution to 5 - 8 °C at a cooling rate of 0.2 - 0.5 °C / min and keep it at 5 - 8 °C for 2 - 3 hours;

[0067] 5. Filter the solid-liquid mixture by suction, take out the precipitate, and wash the precipitate with propanol 8 - 10 times;

[0068] 6. Place the solid-liquid mixture of propanol and sodium carbonate in a ball mill for wet grinding. The material of the grinding balls is selected as stainless steel, the vibration frequency is selected as 240 r / min, and filter after grinding;

[0069] 7. Dry the solid substance at 80 °C for 8 hours, and spherical sodium carbonate N-1 can be obtained after taking it out.

[0070] Example 2

[0071] 1. Add 445.2 g of sodium carbonate powder to 1 L of deionized water for dissolution. At a temperature of 30 - 35 °C and a stirring speed of 60 r / min, obtain a sodium carbonate solution with a concentration of 4.2 mol / L, and stir at a constant speed for 30 minutes;

[0072] 2. Add 2.44 g of anionic surfactant sodium dodecylbenzene sulfonate to deionized water for dissolution. At a temperature of 30 - 35 °C and a stirring speed of 60 r / min, obtain a sodium dodecylbenzene sulfonate solution with a concentration of 0.007 mol / L, and use ammonia water to adjust the pH value of the solution to 7.2 - 11.0, and stir at a constant speed for 30 minutes;

[0073] 3. Under the condition of low-frequency ultrasonic dispersion, at a temperature of 30 - 35 °C and a stirring speed of 60 r / min, slowly add the sodium dodecylbenzene sulfonate solution to the sodium carbonate solution until a trace amount of flocculent precipitate appears, and stir at a constant speed for 60 minutes to obtain a mixed solution;

[0074] 4. Slowly cool the mixed solution to 5 - 8 °C at a cooling rate of 0.2 - 0.5 °C / min and keep it at 5 - 8 °C for 2 - 3 hours;

[0075] 5. Filter the solid-liquid mixture by suction, take out the precipitate, and wash the precipitate with propanol 8 - 10 times;

[0076] 6. Place the solid-liquid mixture of propanol and sodium carbonate in a ball mill for wet grinding. Select zirconia as the material of the grinding balls, choose a vibration frequency of 260 r / min, and filter after grinding.

[0077] 7. Dry the solid substance at 80 °C for 8 hours, and spherical sodium carbonate N-2 can be obtained after taking it out.

[0078] Example 3

[0079] 1. Add 477.0 g of sodium carbonate powder to 1 L of deionized water for dissolution. Under the temperature condition of 30 - 35 °C and at a stirring speed of 60 r / min, obtain a sodium carbonate solution with a concentration of 4.5 mol / L, and stir at a constant speed for 30 minutes.

[0080] 2. Add 2.31 g of anionic surfactant sodium dodecyl sulfate to deionized water for dissolution. Under the temperature condition of 30 - 35 °C and at a stirring speed of 60 r / min, obtain a sodium dodecyl sulfate solution with a concentration of 0.008 mol / L, and use ammonia water to adjust the pH value of the solution to 7.2 - 11.0, and stir at a constant speed for 30 minutes.

[0081] 3. Under the condition of low-frequency ultrasonic dispersion, at a temperature of 30 - 35 °C and at a stirring speed of 60 r / min, slowly add the sodium dodecyl sulfate solution to the sodium carbonate solution until a small amount of flocculent precipitate appears, and stir at a constant speed for 60 minutes to obtain a mixed solution.

[0082] 4. Slowly cool the mixed solution at a cooling rate of 0.2 - 0.5 °C / min to 5 - 8 °C, and keep it at 5 - 8 °C for 2 - 3 hours.

[0083] 5. Filter the solid-liquid mixture by suction filtration, take out the precipitate, and wash the precipitate with propanol 8 - 10 times.

[0084] 6. Place the solid-liquid mixture of propanol and sodium carbonate in a ball mill for wet grinding. Select agate as the material of the grinding balls, choose a vibration frequency of 280 r / min, and filter after grinding.

[0085] 7. Dry the solid substance at 80 °C for 8 hours, and spherical sodium carbonate N-3 can be obtained after taking it out.

[0086] Application Example 1

[0087] The method for synthesizing polyether ether ketone is as follows:

[0088] Nitrogen was continuously introduced into a 3L sealed four-necked flask connected to a water separator, a condenser and a stirrer, and 3492.3g (16mol) of diphenyl sulfone, 440.4g (4.0mol) of hydroquinone, 872.8g (4.0mol) of 4,4-difluorobenzophenone, 508.8g (4.8mol) of sodium carbonate N-1, and 22.1g (0.16mol) of potassium carbonate were added. After the temperature was raised to melt, stirring was started at a speed of 80r / min. It took about 50 minutes to heat from room temperature until the melt stabilized at 180°C. The temperature was maintained at 180°C for 1 hour, and the generated water and gas were separated by a condenser and a separator. Then, the temperature is raised from 180°C to 310°C, which takes about 60 minutes. The temperature is kept constant at 310°C for 1-2 hours. When the torque value of the torque sensor of the stirrer reaches the target value, 4,4'-difluorobenzophenone (10.91g, 0.050mol) is added at one time for end-capping. After another 30 minutes, the mixture in the flask is poured onto a smooth stainless steel plate for cooling. The cooled material is ground (<2mm maximum size), washed with pure acetone for 5-7 times until diphenyl sulfone is no longer detected in the acetone washing liquid, washed with 70°C deionized water for 5-7 times until the conductivity value of the washing liquid is <3μS / cm, and the washed material is placed in a stainless steel tray and placed in an oven at 150°C for 8 hours to obtain a polyetheretherketone product.

[0089] Application Example 2

[0090] The method for synthesizing polyetheretherketone is as follows:

[0091] Nitrogen was continuously introduced into a 3L sealed four-necked flask connected to a water separator, a condenser and a stirrer, and 3492.3g (16mol) of diphenyl sulfone, 440.4g (4.0mol) of hydroquinone, 872.8g (4.0mol) of 4,4-difluorobenzophenone, 508.8g (4.8mol) of sodium carbonate N-2, and 22.1g (0.16mol) of potassium carbonate were added. After the temperature was raised to melt, stirring was started at a speed of 80r / min. It took about 50 minutes to heat from room temperature until the melt stabilized at 180°C. The temperature was maintained at 180°C for 1 hour, and the generated water and gas were separated by a condenser and a separator. Then, the temperature is raised from 180°C to 310°C, which takes about 60 minutes. The temperature is kept constant at 310°C for 1-2 hours. When the torque value of the torque sensor of the stirrer reaches the target value, 4,4'-difluorobenzophenone (10.91g, 0.050mol) is added at one time for end-capping. After another 30 minutes, the mixture in the flask is poured onto a smooth stainless steel plate for cooling. The cooled material is ground (<2mm maximum size), washed with pure acetone for 5-7 times until diphenyl sulfone is no longer detected in the acetone washing liquid, washed with 70°C deionized water for 5-7 times until the conductivity value of the washing liquid is <3μS / cm, and the washed material is placed in a stainless steel tray and placed in an oven at 150°C for 8 hours to obtain a polyetheretherketone product.

[0092] Application Example 3

[0093] The method for synthesizing polyetheretherketone is as follows:

[0094] Nitrogen was continuously introduced into a 3L sealed four-necked flask connected to a water separator, a condenser and a stirrer, and 3492.3g (16mol) of diphenyl sulfone, 440.4g (4.0mol) of hydroquinone, 872.8g (4.0mol) of 4,4-difluorobenzophenone, 508.8g (4.8mol) of sodium carbonate N-3, and 22.1g (0.16mol) of potassium carbonate were added. After the temperature was raised to melt, stirring was started at a speed of 80r / min. It took about 50 minutes to heat from room temperature until the melt stabilized at 180°C. The temperature was maintained at 180°C for 1 hour, and the generated water and gas were separated by a condenser and a separator. Then, the temperature is raised from 180°C to 310°C, which takes about 60 minutes. The temperature is kept constant at 310°C for 1-2 hours. When the torque value of the torque sensor of the stirrer reaches the target value, 4,4'-difluorobenzophenone (10.91g, 0.050mol) is added at one time for end-capping. After another 30 minutes, the mixture in the flask is poured onto a smooth stainless steel plate for cooling. The cooled material is ground (<2mm maximum size), washed with pure acetone for 5-7 times until diphenyl sulfone is no longer detected in the acetone washing liquid, washed with 70°C deionized water for 5-7 times until the conductivity value of the washing liquid is <3μS / cm, and the washed material is placed in a stainless steel tray and placed in an oven at 150°C for 8 hours to obtain a polyetheretherketone product.

[0095] Comparative application example 1

[0096] The method for synthesizing polyetheretherketone is as follows:

[0097] Nitrogen was continuously introduced into a 3L sealed four-necked flask connected to a water separator, a condenser and a stirrer, and 3492.3g (16mol) of diphenyl sulfone, 440.4g (4.0mol) of hydroquinone, 872.8g (4.0mol) of 4,4-difluorobenzophenone, 508.8g (4.8mol) of sodium carbonate (commercially available sodium carbonate S-1), and 22.1g (0.16mol) of potassium carbonate were added. After the temperature was raised to melt, stirring was started at a speed of 80r / min. It took about 50 minutes to heat from room temperature until the melt stabilized at 180°C. The temperature was maintained at 180°C for 1 hour, and the generated water and gas were separated by a condenser and a separator. Then, the temperature is raised from 180°C to 310°C, which takes about 60 minutes. The temperature is kept constant at 310°C for 1-2 hours. When the torque value of the torque sensor of the stirrer reaches the target value, 4,4'-difluorobenzophenone (10.91g, 0.050mol) is added at one time for end-capping. After another 30 minutes, the mixture in the flask is poured onto a smooth stainless steel plate for cooling. The cooled material is ground (<2mm maximum size), washed with pure acetone for 5-7 times until diphenyl sulfone is no longer detected in the acetone washing liquid, washed with 70°C deionized water for 5-7 times until the conductivity value of the washing liquid is <3μS / cm, and the washed material is placed in a stainless steel tray and placed in an oven at 150°C for 8 hours to obtain a polyetheretherketone product.

[0098] Comparative Application Example 2

[0099] The method for synthesizing polyetheretherketone is as follows:

[0100] Continuously introduce nitrogen into a 3L sealed four-necked flask connected to a water separator, a condenser, and a stirrer. Charge 3492.3 g (16 mol) of diphenyl sulfone, 440.4 g (4.0 mol) of hydroquinone, 872.8 g (4.0 mol) of 4,4'-difluorobenzophenone, 508.8 g (4.8 mol) of sodium carbonate (commercially available sodium carbonate S-2), and 22.1 g (0.16 mol) of potassium carbonate. After heating to melting, start stirring at a speed of 80 r / min. It takes about 50 minutes to heat from room temperature to a stable melt temperature of 180 °C. Maintain a constant temperature of 180 °C for 1 hour. The generated water and gas are separated through a condenser and a separator. Then heat from 180 °C to 310 °C, which takes about 60 minutes. Keep the temperature constant at 310 °C for 1 - 2 hours. When the torque value of the torque sensor of the stirrer reaches the target value, add 4,4'-difluorobenzophenone (10.91 g, 0.050 mol) in one portion for end-capping treatment. After another 30 minutes, pour the mixture in the flask onto a smooth stainless-steel plate to cool. Grind and crush the cooled material (<2 mm maximum size). Wash it 5 - 7 times with pure acetone until diphenyl sulfone is no longer detected in the acetone washing solution. Wash it 5 - 7 times with deionized water at 70 °C until the conductivity value of the washing solution <3 μS / cm. Put the washed material into a stainless-steel tray and bake it in an oven at 150 °C for 8 hours to obtain a polyetheretherketone product.

[0101] Comparative Application Example 3

[0102] The method for synthesizing polyetheretherketone is as follows:

[0103] Nitrogen was continuously introduced into a 3L sealed four-necked flask connected to a water separator, a condenser and a stirrer, and 3492.3g (16mol) of diphenyl sulfone, 440.4g (4.0mol) of hydroquinone, 872.8g (4.0mol) of 4,4-difluorobenzophenone, 508.8g (4.8mol) of sodium carbonate (commercially available sodium carbonate S-3), and 22.1g (0.16mol) of potassium carbonate were added. After the temperature was raised to melt, stirring was started at a speed of 80r / min. It took about 50 minutes to heat from room temperature until the melt stabilized at 180°C. The temperature was maintained at 180°C for 1 hour, and the generated water and gas were separated by a condenser and a separator. Then, the temperature is raised from 180°C to 310°C, which takes about 60 minutes. The temperature is kept constant at 310°C for 1-2 hours. When the torque value of the torque sensor of the stirrer reaches the target value, 4,4'-difluorobenzophenone (10.91g, 0.050mol) is added at one time for end-capping. After another 30 minutes, the mixture in the flask is poured onto a smooth stainless steel plate for cooling. The cooled material is ground (<2mm maximum size), washed with pure acetone for 5-7 times until diphenyl sulfone is no longer detected in the acetone washing liquid, washed with 70°C deionized water for 5-7 times until the conductivity value of the washing liquid is <3μS / cm, and the washed material is placed in a stainless steel tray and placed in an oven at 150°C for 8 hours to obtain a polyetheretherketone product.

[0104] Comparative Example 1

[0105] The method for preparing spherical sodium carbonate in this comparative example is basically the same as that in Example 1, except that: in step 6, the solid-liquid mixture of propanol and sodium carbonate is dried in a fume hood, and the dried sodium carbonate is placed in a ball mill for dry grinding, the material of the grinding ball is zirconium oxide, the vibration frequency is 260 r / min, and the other conditions are the same as those in Example 1, to prepare spherical sodium carbonate D-1;

[0106] Without grinding in step 6, other conditions were the same as in Example 1 to prepare spherical sodium carbonate D-1.

[0107] Comparative Example 2

[0108] The method for preparing spherical sodium carbonate in this comparative example is basically the same as that in Example 1, except that: in step 4, room temperature crystallization is used instead of the original low temperature crystallization;

[0109] Other conditions were the same as those in Example 1 to prepare spherical sodium carbonate D-2.

[0110] Comparative Application Example 4

[0111] In this comparative application example, the method for synthesizing polyetheretherketone is basically the same as that in Application Example 1, except that the spherical sodium carbonate D-1 prepared in Comparative Example 1 is used, and other conditions remain unchanged to prepare polyetheretherketone.

[0112] Comparative Application Example 5

[0113] In this comparative application example, the method for synthesizing polyether ether ketone is basically the same as that in Application Example 1, except that spherical sodium carbonate D-2 prepared in Comparative Example 2 is used, and other conditions remain unchanged to prepare polyether ether ketone.

[0114] Test Example

[0115] The polyether ether ketone or spherical sodium carbonate of the above embodiments and comparative examples of the present invention was tested by the following test methods. The specific methods are as follows:

[0116] (1) Test of molecular weight distribution: Using an Agilent Technologies PL-GPC220 High Temperature Chromatograph, with α-chloronaphthalene as the solvent and 1,2,4-trichlorobenzene as the diluent. The column temperature is 125 °C, and the mobile phase uses a mixture of α-chloronaphthalene and 1,2,4-trichlorobenzene, and their mass ratio is α-chloronaphthalene:1,2,4-trichlorobenzene = 1:2.2. The test parameters are taken as K = 14.2 and α = 0.72.

[0117] (2) Test of melt viscosity MV: Using a Dynisco LCR 7001 capillary rheometer, the test temperature is 400 °C, the load is 10 KN, and the shear flow rate at 1000 (1 / S) is taken as the test result;

[0118] (3) Mechanical property test: After injection molding into standard test specimens by an injection molding machine, a Shimadzu AG-Xplus universal testing machine and a notched impact testing machine are used to measure the notched impact strength, tensile strength, elongation at break, flexural strength, and flexural modulus of the polymer material according to the ISO527 method. Each sample is tested 5 times and the average value is taken.

[0119] (4) Colorimetric test: Using a color difference meter to measure the L value, a value, and b value of the sample;

[0120] (5) Thermal stability: Using thermogravimetric analysis TGA to characterize the thermal stability of polyether ether ketone resin. Among them, the initial decomposition temperature measured by thermogravimetric analysis TGA is used to characterize the thermal stability of polyether ether ketone resin because the initial decomposition temperature is the temperature at which the TGA curve starts to deviate from the baseline point and has good repeatability.

[0121] (6) Using a laser particle size distribution analyzer to test the particle size distribution of spherical sodium carbonate.

[0122] (7) Using a scanning electron microscope to observe the microscopic morphology of spherical sodium carbonate.

[0123] (8) The specific surface area of sodium carbonate was measured using a fully automatic specific surface area and pore size distribution analyzer from Quantachrome Instruments, USA.

[0124] (9) The roundness of spherical sodium carbonate was measured using a dynamic image particle size and shape analyzer.

[0125] Table 1 Mechanical property test results of polyetheretherketone resin: impact strength, tensile strength, elongation at break, flexural strength, flexural modulus

[0126]

[0127] As can be seen from Table 1, the performance of the example samples in terms of conventional mechanical properties such as impact strength, tensile strength, elongation at break, flexural strength, and flexural modulus is superior to that of the comparative example samples.

[0128] Table 2 Particle size distribution test of spherical sodium carbonate prepared in Example 1 / 2 / 3

[0129]

[0130] As can be seen from Table 2, the example samples have a high degree of sphericity (minimum roundness greater than 0.8, average roundness above 0.9) and a large specific surface area.

[0131] Table 3 Polymerization reaction time of examples and comparative examples

[0132] Polymerization reaction time / minute Application Example 1 217 Application Example 2 221 Application Example 3 224 Comparative Application Example 1 266 Comparative Application Example 2 272 Comparative Application Example 3 269 Comparative Application Example 4 273 Comparative Application Example 5 281

[0133] As can be seen from Table 3, there are significant differences in the polymerization reaction time between the application examples and the comparative application examples, and the polymerization reaction time of the application examples is shortened by about 20%.

[0134] Table 4 Color test results of polyetheretherketone resin

[0135]

[0136]

[0137] As can be seen from Table 4, the L value, a value, and b value of the example samples are significantly better than those of the comparative example samples.

[0138] Table 5 Molecular weight distribution of polyetheretherketone resin: polydispersity index PDI = Mw / Mn

[0139] Sample Polydispersity index PDI Application Example 1 3.82 Application Example 2 3.78 Application Example 3 3.69 Comparative Application Example 1 3.75 Comparative Application Example 2 3.81 Comparative Application Example 3 3.63 Comparative Application Example 4 3.72 Comparative Application Example 5 3.65

[0140] As can be seen from Table 5, the polymerization reaction time of the present invention is significantly shortened, the production efficiency gain is remarkable, the prepared polyetheretherketone resin does not have a decrease in performance or color due to the change in the polymerization reaction time, and moreover, the molecular weight distribution of the prepared polyetheretherketone resin does not have an obvious difference due to the change in the polymerization reaction time.

[0141] Table 6 Thermal stability of polyetheretherketone resin

[0142] Sample Initial decomposition temperature Test atmosphere Temperature range Heating rate Application Example 1 594.7 20% oxygen + 80% nitrogen 40-800℃ 20°C / min Application Example 2 595.5 20% oxygen + 80% nitrogen 40-800℃ 20°C / min Application Example 3 594.8 20% oxygen + 80% nitrogen 40-800℃ 20°C / min Comparative Application Example 1 572.2 20% oxygen + 80% nitrogen 40-800℃ 20°C / min Comparative Application Example 2 572.5 20% oxygen + 80% nitrogen 40-800℃ 20°C / min Comparative Application Example 3 571.1 20% oxygen + 80% nitrogen 40-800℃ 20°C / min

[0143] As can be seen from Table 6, the thermal stability performance of the example samples is significantly better than that of the comparative example samples.

[0144] The above describes the exemplary embodiments of the present invention. However, the protection scope of this application is not limited to the above embodiments. Any modifications, equivalent replacements, improvements, etc. made by those skilled in the art within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A spherical sodium carbonate, characterized in that The particle size distribution of the spherical sodium carbonate includes: D50 is 100-250 μm, D90 is 250-400 μm; The specific surface area of ​​the spherical sodium carbonate is 0.5-3.5m 2 / g; The circularity of the spherical sodium carbonate is greater than 0.

8.

2. Spherical sodium carbonate according to claim 1, characterized in that, The circularity of the spherical sodium carbonate is greater than 0.

9.

3. The preparation method of spherical sodium carbonate according to claim 1 or 2, characterized in that, The preparation method comprises: mixing a sodium carbonate solution and a surfactant solution to obtain a mixed solution, cooling the mixed solution to 5-8°C at a cooling rate of 0.2-0.5°C / min, reacting at 5-8°C for 2-3 hours to obtain a solid-liquid mixture, filtering to obtain a solid substance, and performing wet grinding to obtain the spherical sodium carbonate.

4. The preparation method according to claim 3, characterized in that: The sodium carbonate solution is an aqueous solution of sodium carbonate, and its concentration is 4.0-4.5 mol / L; And / or, the surfactant solution comprises an anionic surfactant and water, wherein the concentration of the anionic surfactant is 0.005-0.01 mol / L; the pH of the surfactant solution is greater than 7; And / or, the anionic surfactant is selected from at least one of alkyl sulfates, alkyl phosphates, alkyl sulfonates, alkyl naphthalene sulfonates or alkyl benzene sulfonates with a carbon chain length of C1 to C18.

5. The preparation method according to claim 3, characterized in that: The specific process of mixing the sodium carbonate solution and the surfactant solution to obtain the mixed solution is as follows: under the temperature condition of 30-35° C., under the condition of low-frequency ultrasonic dispersion and stirring, the surfactant solution is added dropwise to the sodium carbonate solution until a trace amount of flocculent precipitation appears, and the addition is stopped and stirring is continued to obtain the mixed solution; And / or, the wet grinding specifically refers to: mixing the solid substance and the alcohol solvent and placing them in a ball mill for wet grinding; the material of the grinding balls in the ball mill is selected from at least one of stainless steel, hard steel, agate, and zirconia; the vibration frequency of the ball mill is 100-500r / min.

6. Use of the spherical sodium carbonate according to claim 1 or 2 in the preparation of polyetheretherketone resin.

7. A polyetheretherketone resin, characterized in that The polyetheretherketone resin is prepared by using the spherical sodium carbonate described in claim 1 or 2.

8. The polyetheretherketone resin according to claim 7, characterized in that The molecular weight distribution PDI of the polyetheretherketone resin is 3.0 to 5.0; And / or, the mechanical properties of the polyetheretherketone resin are as follows: impact strength is 8 to 10 KJ / m 2 ; Tensile strength is not less than 90MPa; Elongation at break is more than 70%; Flexural strength is not less than 140MPa; Flexural modulus is not less than 3400MPa; And / or, the polyetheretherketone resin has thermal stability; And / or, in the chromaticity of the polyetheretherketone resin, the L value is greater than 70; the a value is 1-4; and the b value is not greater than 10.

9. A method for preparing the polyetheretherketone resin according to claim 7 or 8, characterized in that: The method comprises the following steps: (1) Under the protection of an inert gas, the spherical sodium carbonate according to claim 1 or 2, bisphenol, and an organic dihalide are mixed to obtain a mixture; (2) heating the mixture obtained in step (1) to a molten state, and then heating to a polymerization reaction temperature to carry out a polymerization reaction; (3) adding an organic halide to step (2) for end-capping treatment to obtain a reaction product; (4) Cooling, crushing, purifying and drying the reaction product obtained in step (3) to obtain the polyetheretherketone resin.

10. Use of the polyetheretherketone resin according to claim 7 or 8 in aerospace, medical treatment, electronic appliances, automobile manufacturing, and petrochemical industry.

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