Preparation method of polyether-ether-ketone

Abstract

The invention discloses a preparation method of polyether-ether-ketone. The preparation method of the polyether-ether-ketone comprises the step of preparing the polyether-ether-ketone in the presence of carbonate and / or bicarbonate of alkali metal, wherein the D90 of the carbonate and / or bicarbonate of the alkali metal is less than 45 [mu] m. Under the condition of reduced pressure operation, when carbonate and / or bicarbonate of alkali metal with D90 smaller than 45 microns are / is used for preparing polyether-ether-ketone, polyether-ether-ketone with properties (such as color, mechanical property and the like) equivalent to those of a conventional process can be obtained, and the gel content is lower.

Description

Technical Field

[0001] The present invention relates to a method for preparing polyetheretherketone polymers and belongs to the field of polymer preparation processes. Background Art

[0002] Polyetheretherketone (PEEK) is a polymer with a repeating unit containing a ketone bond and two ether bonds in the main chain. It has excellent properties such as high temperature resistance, chemical resistance, high strength, and / or high wear resistance, and belongs to special polymer materials. The application fields of polyetheretherketone are very wide. In the aerospace field, due to its characteristics of low density, high strength, and high temperature resistance, it is widely used in manufacturing components such as aircraft engine parts, missiles, and satellites. In the medical field, the biocompatibility of polyetheretherketone makes it an ideal material for artificial organs. In addition, polyetheretherketone also has wide applications in industrial fields such as electronic appliances, automobile manufacturing, and petrochemical industry.

[0003] Although in the existing preparation methods of polyether ketone compounds, it is usually necessary to carry out a reaction in the presence of an alkali metal carbonate or bicarbonate to prepare polyetheretherketone. However, despite many studies in the prior art, due to the different structures of the monomers as reaction substrates and the synthesized polymers, the research conclusions of the inventors on the particle size of carbonates or bicarbonates vary greatly. For example, in patent document US4,636,557, the particle size of potassium carbonate is only controlled within the range of less than 0.3 mm; patent document US5,081,214 uses a mixture of sodium carbonate and sodium bicarbonate with a particle size of 200 - 800 μm; patent document US5,194,561 recommends using sodium carbonate with a smaller particle size when preparing aromatic polyethers containing carbonyl or sulfonyl groups. However, for the process of polyetheretherketone, patent document CN102257034B emphasizes that the reactivity of different monomers has different requirements for the particle size of carbonates or bicarbonates, and strongly recommends that in the preparation process of polyetheretherketone, the particle size D of sodium carbonate 90 ≥45 μm should be controlled, and "too fine" Na2CO3 should be avoided, otherwise it will lead to a difficult-to-handle low bulk density and a difficult-to-control synthesis reaction kinetics.

[0004] Therefore, there is still a need to develop an improved method for preparing polyetheretherketone, so as to improve its process efficiency and economy, and improve the quality of the product. Summary of the Invention

[0005] To solve the above technical problems, the present invention provides a method for preparing polyetheretherketone, the preparation method comprising preparing polyetheretherketone in the presence of an alkali metal carbonate and / or bicarbonate;

[0006] wherein, the D of the alkali metal carbonate and / or bicarbonate 90 <45 μm.

[0007] According to an embodiment of the present invention, the preparation method includes reacting a carbonate and / or bicarbonate of an alkali metal with a bisphenol and an organic dihalide, and then end-capping the reaction product to obtain polyether ether ketone.

[0008] According to an embodiment of the present invention, the preparation method includes the following steps:

[0009] S1: Under nitrogen protection, mixing a carbonate and / or bicarbonate of an alkali metal, a bisphenol, and a solvent to obtain a mixture;

[0010] S2: Performing a depressurization operation on the mixture obtained in step S1, and then reacting under heating conditions;

[0011] S3: Mixing and reacting the material after the reaction in step S2 with an organic dihalide;

[0012] S4: Adding an organic halide to perform end-capping treatment in step S3 to obtain a reaction product;

[0013] S5: Cooling, pulverizing, purifying, and drying the reaction product obtained in step S4 to obtain the polyether ether ketone.

[0014] According to an embodiment of the present invention, the alkali metal is selected from potassium and / or sodium.

[0015] According to an embodiment of the present invention, the alkali metal carbonate is selected from sodium carbonate.

[0016] According to an embodiment of the present invention, the D of the carbonate and / or bicarbonate of the alkali metal 90 ≤40 μm, for example ≤38 μm, such as ≤35 μm, such as ≤30 μm, and its examples can be 1 - 40 μm, or 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, or 40 μm.

[0017] According to an embodiment of the present invention, the molar ratio of the carbonate and / or bicarbonate of the alkali metal to the bisphenol is (1.003 - 1.17):1, for example 1.1:1.

[0018] 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.

[0019] According to an embodiment of the present invention, the solvent is an aromatic sulfone, and the aromatic sulfone is selected from at least one of diphenyl sulfone, dibenzothiophene dioxide, phenoxathiin dioxide, and 4-phenylsulfonyl biphenyl, and preferably diphenyl sulfone.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] According to an embodiment of the present invention, in step S2, the reaction conditions include: reducing the pressure to a vacuum gauge pressure less than -0.01 MPa, for example, -0.05 MPa; and the temperature is 115 - 125 °C.

[0024] According to an embodiment of the present invention, in step S3, the reaction temperature is 250 - 320 °C (for example, 250 °C, 300 °C).

[0025] According to an embodiment of the present invention, in step S4, 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 1-6 alkyloxy (such as methoxy, ethoxy, propoxy, isopropoxy), and its examples can be 4-fluorobenzophenone, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 2,4'-difluorobenzophenone, 4-fluoro-4'-methoxybenzophenone.

[0026] According to an embodiment of the present invention, in step S4, the conditions of the end-capping treatment include: the temperature is 295 - 320 °C; and the time is 15 - 45 min.

[0027] According to an embodiment of the present invention, in step S5, the cooling can be carried out by a method known in the art. For example, the reaction product is placed on a metal plate (such as a stainless steel plate) for cooling.

[0028] According to an embodiment of the present invention, in step S5, 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.

[0029] According to an embodiment of the present invention, in step S5, the purification includes first washing the powder particles with an organic solvent and then performing multiple water washes.

[0030] 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 S1), 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, when washing, the organic solvent is selected from organic solvents miscible with water, such as acetone.

[0031] 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 50 - 60 °C.

[0032] Preferably, the number of times of the water wash is not specifically limited, as long as the conductivity of the filtered water is less than 10 μS / cm after rinsing.

[0033] According to an embodiment of the present invention, in step S5, the drying can be carried out by a method known in the art, as long as the polyether ether ketone after water wash can be dried.

[0034] The present invention also provides polyether ether ketone obtained by the above preparation method.

[0035] According to an embodiment of the present invention, the polyether ether ketone has at least one of the following properties:

[0036] 1) The gel content is not more than 0.7%, such as 0.47%, 0.62%, 0.32%, 0.37%;

[0037] 2) The melt index is not more than 20 g / 10 min, such as 14.35 g / 10 min, 15.68 g / 10 min;

[0038] 3) The molecular weight distribution PDI is not more than 2.5, such as 2.2, 2.3;

[0039] 4) The viscosity is not less than 350 Pa·s, for example, it is 367.4 Pa·s, 361.1 Pa·s;

[0040] 5) The glass transition temperature Tg is at least 143 °C;

[0041] 6) The melting point Tm is at least 330 °C, for example, it is 334 °C.

[0042] According to the embodiments of the present invention, the mechanical properties of the polyetheretherketone are as follows: the flexural strength is not less than 140 MPa, for example, it is 146.72 MPa, 147.30 MPa; the flexural modulus is not less than 3500 MPa, for example, it is 3516.71 MPa, 3520.04 MPa.

[0043] According to the embodiments of the present invention, in the chromaticity of the polyetheretherketone, the L value is not less than 70, for example, it is 78.67, 78.50; the a value is not more than 3, for example, it is 2.49, 2.29, 2.88; the b value is not more than 8, for example, it is 6.11, 7.15.

[0044] The present invention also provides the application of the above polyetheretherketone polymer in the fields of aerospace, medical treatment, electronic appliances, automobile manufacturing, petrochemical industry, etc., for example, the application in film products.

[0045] Beneficial effects

[0046] The inventors surprisingly found that, different from the teachings in the patent document CN102257034B, under the conditions of reduced-pressure operation, when carbonates and / or bicarbonates of alkali metals with D 90 <45 μm are used to prepare polyetheretherketone, polyetheretherketone with properties (such as color, mechanical properties, etc.) equivalent to those of the conventional process can be obtained, and the gel content is lower. Specific embodiments

[0047] The technical solutions of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only for illustrative explanation 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.

[0048] Unless otherwise specified, the raw materials and reagents used in the following embodiments are all commercially available products or can be prepared by known methods.

[0049] The test methods for the following embodiments are as follows:

[0050] 1. Test method for the viscosity of polyetheretherketone

[0051] In the present invention, the viscosity is the ratio of shear stress to shear rate, and the unit is Pa·s.

[0052] In the present invention, the method for measuring the fluidity of plastics using a capillary rheometer, which can also be called a method for testing apparent viscosity, is carried out according to the standard of GB / T 25278-2010 using a Dynisco laboratory capillary rheometer LCR7001.

[0053] The dimensions of the capillary die of the equipment used for testing are as follows: 1 mm in diameter and 20 mm in length, and the ratio of the length to the diameter (L / D) of the die is 20.

[0054] In the present invention, the specific steps of the method for testing viscosity are as follows:

[0055] (1) Before measurement, the test sample (polyetheretherketone) is pretreated according to the provisions of GB / T2918-1998, that is, the test sample is placed in an environment with a temperature of 23±2°C and a humidity of 50±10% for 24±0.5 hours and then reserved for use;

[0056] (2) Before testing, each component of the test instrument reaches thermal equilibrium at the test temperature (the test temperature is 400°C), and then charging starts: 10-15 g of the test sample in step (1) is added to the barrel in small portions (charged to about 12.5 mm from the top of the barrel), and immediately compacted with a plunger to prevent air from being introduced, and the charging is completed within 2 minutes;

[0057] (3) Immediately after the charging is completed, the preheating timing starts, and the preheating is carried out for 5 minutes. Subsequently, the melt of the test sample is extruded through a capillary die with known dimensions, and under the condition of a certain volume flow rate, the test pressure (i.e., shear stress) is measured; the test conditions are a test temperature of 400°C and a shear rate of 1000 s -1 .

[0058] 2. Gel test method

[0059] The method for gel test is as follows:

[0060] Using a sintered glass funnel, place a 40 ml G4 sintered glass funnel in an oven at a constant temperature of 150 °C for 8 hours. After cooling, take it out and let it stand. Weigh the weight W1 of the sintered glass funnel using an analytical balance; Take 0.1 g of PEEK sample with an analytical balance and put it into a reagent bottle, add 5 ml of 4-chlorophenol, then place it in a shaker and shake at a constant temperature of 180 °C for 2 h. After complete dissolution without residues, place it on the operating table and cool to room temperature, then add 1,2,4-trichlorobenzene and let it stand for 5 min; Pour 5 groups of solutions of the same batch into the sintered glass funnel for suction filtration, then take 10 ml of 4-chlorophenol to wash the reagent bottle and the sintered glass funnel, and perform suction filtration. Next, wash the sintered glass funnel with 25 ml of anhydrous ethanol and perform suction filtration. Finally, place it in an oven and dry for 2 h. After cooling, take out the funnel and weigh it with an analytical balance as W2; Calculate the percentage content of the PEEK gel according to the formula (W2 - W1) / 0.5 g × 100%.

[0061] 3. Chromaticity test method:

[0062] The chromaticity test is measured using the NR200 portable computer colorimeter of Shenzhen 3nh Technology Co., Ltd. Inject the material into a sample plate of 60 mm * 60 mm * 2 mm. Place the test port of the NR200 portable computer colorimeter horizontally on the smooth side of the sample plate. Ensure a good surface fit and then conduct the test. Take the average value after testing five times as the chromaticity.

[0063] 4. Bending property test method:

[0064] Conduct according to the method specified in GB / T 9341 2008 Plastics - Determination of flexural properties. Among them, the specimen size has a length of 80 mm ± 2 mm, a width of 10 mm ± 2 mm, and a thickness of 4 mm ± 2 mm, and the test speed is 2 mm / min.

[0065] 5. Test of melt index:

[0066] The melt mass - flow rate is based on the GB / T3682.1 - 2018 standard. The mass extruded in a specified time (such as 10 min) is used as the melt mass - flow rate, and the unit is g / 10 min. Measure using the SRZ - 400E melt flow rate tester of Changchun Intelligent Instrument and Equipment Co., Ltd. The die of the equipment used has the following dimensions: a diameter of 2.095 ± 0.005 mm and a length of 8.000 ± 0.025 mm.

[0067] The test method of the melt index of the present invention specifically includes:

[0068] (1) Before the test, the barrel and the piston are kept at a constant temperature for at least 15 minutes at the test temperature;

[0069] (2) The amount of material added to the barrel is 3 - 8 g of polymer. Loading is completed within 1 minute. After loading is completed, preheating is immediately started for 5 minutes. During preheating, it is necessary to confirm that the temperature of the equipment has returned to the set test temperature value.

[0070] (3) Subsequently, tests are carried out under the conditions of a test temperature of 380 °C and a load of 5 kg. The melt of the test sample is extruded from the die within the specified time. When the specified time is reached, the melt strip is cut off. The length of the cut strip is 10 - 20 mm. All strips with visible bubbles are discarded and cooled.

[0071] (4) Repeat the above steps (1)-(3) N times (N is not less than 3). When at least N strips are obtained, weigh them one by one, accurate to 1 mg, and calculate the average mass M of the strips, and input it into the machine to obtain the melt index, with the unit g / 10min.

[0072] 6. Molecular weight distribution test method

[0073] The steps for testing the molecular weight of PEEK by gel permeation chromatography are as follows:

[0074] First, prepare the mobile phase. The mobile phase is selected to use 1,2,4-trichlorobenzene and 4-chlorophenol; dissolve PEEK. Dissolve 0.1 g of PEEK in 5 ml of 4-chlorophenol; cover the reagent bottle with an aluminum cap and place it on a heating oscillator at a temperature of 180 °C and heat until completely dissolved; cool the reagent bottle to room temperature, add 5 ml of 1,2,4-trichlorobenzene, and filter the solution through a 0.45 μm glass fiber filter using a syringe; perform gel permeation chromatography on the filtrate and analyze the obtained data to obtain the molecular weight distribution data.

[0075] Example 1

[0076] The preparation method of polyetheretherketone includes the following steps:

[0077] (1) Prepare the polyetheretherketone crude product:

[0078] Use a 5 L stainless steel reaction kettle equipped with a nitrogen protection device, a feed inlet, a vacuum pumping device, a thermocouple temperature detection device, a stirrer, and a stirring paddle. Add 2135 g (9.78 mol) of diphenyl sulfone to the reaction kettle, and finely ground sodium carbonate (D 90≤40 μm) 367.82 g (3.47 mol), hydroquinone 335 g (3.04 mol). Nitrogen was introduced for protection for 1 h, and then vacuum was pumped. When the pressure gauge showed -0.05 Mpa, heating was started at a heating rate of 4 °C / min. After the temperature reached 120 °C, it was kept constant for 120 min. Stirring was started, and then the temperature was raised to 140 °C at a heating rate of 2 °C / min. Nitrogen was continuously introduced while stopping vacuum pumping to restore normal pressure inside. At this time, 674.24 g (3.09 mol) of 4,4-difluorobenzophenone was added to the reaction kettle, and the temperature was raised to 180 °C at a heating rate of 2 °C / min and kept constant for 60 min; then

[0079] the temperature was raised to 190 °C at a heating rate of 1 °C / min and kept constant for 30 min; then the temperature was raised to 200 °C at a heating rate of 0.5 °C and kept constant for 30 min; then the temperature was raised to 280 °C at a heating rate of 1 °C / min and kept warm at this temperature for 60 min. Finally, the temperature was raised to 300 °C at a heating rate of 1 °C / min. After keeping it for 60 min, 2.01 g (0.01 mol) of 4-fluorobenzophenone was added to the reaction kettle for capping, and stirring was continued for 30 min to obtain the product, which was the crude polyetheretherketone product.

[0080] After that, the obtained product was spread flat on a stainless steel plate and waited to solidify and cool to room temperature to obtain the solidified product. Subsequently, the solidified product was crushed and sieved using a pulverizer, and the powder particles with a mesh number between 15 and 60 were selected, which were the powder particles of the crude polyetheretherketone product.

[0081] (2) Purification

[0082] The above powder particles were purified: The powder particles were added to acetone solvent, and the reaction solvent diphenyl sulfone and other remaining organic impurities in the above powder particles were dissolved in the solvent, and then repeatedly extracted with a Soxhlet extractor for 1 hour to obtain the filtered powder particles.

[0083] (3) Washing with water

[0084] Then the above filtered powder particles were washed with water: The above filtered powder particles were added to purified water and stirred and washed. After heating and raising the temperature to 60 °C, the deionized water was filtered out, and then rinsed with ultrapure water (conductivity not greater than 1 μS / cm) and then heated and stirred again. Washing was repeated more than 4 times until the conductivity of the ultrapure water after rinsing was between 2 and 10 μS / cm. The powder particles after washing with water were put into a vacuum drying oven and dried at a constant temperature of 150 °C for 8 h to obtain polyetheretherketone.

[0085] Comparative Example 1

[0086] A 5L stainless steel reactor is used, equipped with a nitrogen protection device, a feed inlet, a thermocouple temperature detection device, a stirrer, and a stirring paddle. Add 2135 g (9.78 mol) of diphenyl sulfone, finely ground sodium carbonate (D90 = 250 μm)

[0087] 367.82 g (3.47 mol), 9.67 g (0.07 mol) of potassium carbonate, 335 g (3.04 mol) of hydroquinone, 674.24 g (3.09 mol) of 4,4'-difluorobenzophenone. Pass nitrogen for protection for 1 h, then start heating with a heating rate of 4 °C / min. After the temperature rises to 140 °C, start stirring, and raise the temperature to 180 °C at a heating rate of 2 °C / min, and keep the temperature constant for 60 min; then

[0088] raise the temperature to 190 °C at a heating rate of 1 °C / min and keep the temperature constant for 30 min; then raise the temperature to 200 °C at a heating rate of 0.5 °C and keep the temperature constant for 30 min; then immediately raise the temperature to 280 °C at a heating rate of 1 °C / min and keep the temperature at this level for 60 min. Finally, raise the temperature to 300 °C at a heating rate of 1 °C / min, keep it for 60 min, and then add 2.01 g of 4-fluorobenzophenone to the reaction kettle for end-capping. Keep stirring for 30 min.

[0089] Then pour the obtained product flat on a stainless steel plate and wait for it to solidify and cool to room temperature. Crush the obtained reactants using a pulverizer, sieve them, and select the powder with particle sizes between 15 and 60 mesh. Use a Soxhlet extractor, with acetone as the solvent, to extract the reaction solvent diphenyl sulfone and other remaining organic impurities in the powder particles, and extract repeatedly for 1 hour. Then stir and wash the filtered particles with purified water. When heating, pour out the deionized water after the temperature rises to 60 °C, rinse with ultrapure water, and then heat and stir again, repeating more than 4 times until the conductivity is between 2 and 10 μS. Put the product after water washing into a vacuum drying oven, set the temperature in the chamber to 150 °C, and dry at a constant temperature for 8 h.

[0090] Comparative Example 2

[0091] Use a 5L stainless steel reactor, equipped with a nitrogen protection device, a feed inlet, a vacuum pumping device, a thermocouple temperature detection device, a stirrer, and a stirring paddle. Add 2135 g (9.78 mol) of diphenyl sulfone, finely ground and sieved sodium carbonate (D 90≤40 μm) 367.82 g (3.47 mol), hydroquinone 335 g (3.04 mol), nitrogen was introduced for protection for 1 h, and then the temperature was raised to 140 °C at a heating rate of 4 °C / min; stirring was started. 674.24 g (3.09 mol) of 4,4-difluorobenzophenone was added to the reaction kettle, and the temperature was raised to 180 °C at a heating rate of 2 °C / min and kept at a constant temperature for 60 min; then

[0092] the temperature was raised to 190 °C at a heating rate of 1 °C / min and kept at a constant temperature for 30 min; then the temperature was raised to 200 °C at a heating rate of 0.5 °C and kept at a constant temperature for 30 min; then the temperature was raised to 280 °C at a heating rate of 1 °C / min and kept at this temperature for 60 min. Finally, the temperature was raised to 300 °C at a heating rate of 1 °C / min, and after keeping it for 60 min, 2.01 g of 4-fluorobenzophenone was added to the reaction kettle for capping. Stirring was continued for 30 min.

[0093] After that, the obtained product was poured and spread flat on a stainless steel plate and waited to solidify and cool to room temperature. The obtained reactant was crushed with a crusher, sieved, and the powder with a mixture particle size between 15 and 60 mesh was selected. Using a Soxhlet extractor, acetone was used as the solvent to extract the reaction solvent diphenyl sulfone and other remaining organic impurities in the powder particles, and extraction was repeated for 1 hour. Then the filtered particles were stirred and washed with purified water. When heated to 60 °C, the deionized water was poured out, rinsed with ultrapure water, and then heated and stirred again, repeated more than 4 times until the conductivity was between 2 and 10 μS. The product after washing with water was put into a vacuum drying oven, the temperature in the chamber was set to 150 °C, and dried at a constant temperature for 8 h.

[0094] Comparative Example 3

[0095] The preparation method of polyetheretherketone in this comparative example was basically the same as that in Example 1, except that: the sodium carbonate with D 90 ≤40 μm was replaced with sodium carbonate with D 90 = 50 μm.

[0096] Comparative Example 4

[0097] The preparation method of polyetheretherketone in this example was basically the same as that in Example 1, except that: the pressure of vacuum pumping was changed to -0.02 Mpa.

[0098] Test Example 1

[0099] The polyether ether ketones obtained from the above-mentioned examples and comparative examples were respectively made into test samples, and the flexural properties were tested according to the method specified in GB / T 9341-2008 Plastics - Determination of flexural properties. The dimensions of the specimens were as follows: length 80 mm ± 2 mm, width 10 mm ± 2 mm, thickness 4 mm ± 2 mm, and the test speed was 2 mm / min.

[0100] The results were summarized in Table 3.

[0101] Test Example 2

[0102] The polyether ether ketones obtained from the above-mentioned examples and comparative examples were respectively made into samples, and the colorimetric test was carried out with reference to the above method. Among them, the dimensions of the samples were as follows: length 60 mm ± 2 mm, width 60 mm ± 2 mm, thickness 2 mm ± 0.5 mm.

[0103] The results were summarized in Table 3.

[0104] Test Example 3

[0105] 1. The polyether ether ketones obtained from the examples and comparative examples were respectively taken to test the melt index (abbreviation: MI) and viscosity with reference to the above method, and the results were summarized in Table 1;

[0106] The polyether ether ketones obtained from the examples and comparative examples were respectively taken to test the molecular weight distribution (PDI) and gel content with reference to the above method, and the results were summarized in Table 2.

[0107] Table 1: Data table of melt index and viscosity

[0108] Melt Index (g / 10 min) Viscosity (Pa·s) Example 1 14.35 367.4 Comparative Example 1 15.68 361.1 Comparative Example 2 1.36 113.1 Comparative Example 3 29.87 312.2 Comparative Example 4 32.26 298.7

[0109] Table 2: Data table of molecular weight distribution and gel content

[0110] Molecular Weight Distribution (PDI) Gel Content (%) Example 1 2.2 0.47 Comparative Example 1 2.1 0.62 Comparative Example 2 2.2 0.72 Comparative Example 3 2.2 0.37 Comparative Example 4 2.2 0.42

[0111] Table 3: Data table of flexural properties and colorimetric values

[0112]

[0113]

[0114] It can be seen from Tables 1 - 3 that:

[0115] The melt index and viscosity of the polyether ether ketone prepared by using sodium carbonate with D90 ≤ 40 μm in the present invention are basically equivalent to those of the polyether ether ketone prepared by conventionally using sodium carbonate with D90 > 45 μm in Comparative Example 1, and produce less gel content, and its mechanical properties and colorimetric values are basically the same as those in Comparative Example 1 using the conventional process.

[0116] In Comparative Example 2, only decompression conditions were adopted, and in Comparative Example 3, only sodium carbonate with D90 ≤ 40 μm was used. Although the resulting polyether ether ketone had a lower gel content, its mechanical properties were lower, the L value of the chromaticity was lower, the b value was higher, and its melt index or viscosity could not meet the product requirements.

[0117] The exemplary embodiments of the present invention have been described above. 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 preparation method of polyetheretherketone, characterized in that, The preparation method includes preparing polyetheretherketone in the presence of a carbonate and / or bicarbonate of an alkali metal; Among them, the D of the carbonate and / or bicarbonate of the alkali metal 90 < 45 μm.

2. The preparation method according to claim 1, wherein, The preparation method includes reacting a carbonate and / or bicarbonate of an alkali metal with a bisphenol and an organic dihalide, and then subjecting the reaction product to end-capping treatment to prepare polyetheretherketone.

3. The preparation method according to claim 1, characterized in that, The preparation method includes the following steps: S1: Under nitrogen protection, mixing a carbonate and / or bicarbonate of an alkali metal, a bisphenol, and a solvent to obtain a mixture; S2: Subjecting the mixture obtained in step S1 to a pressure reduction operation, and then reacting under heating conditions; S3: Mixing and reacting the material after the reaction in step S2 with an organic dihalide; S4: Adding an organic halide to step S3 for end-capping treatment to obtain a reaction product; S5: Cooling, pulverizing, purifying, and drying the reaction product obtained in step S4 to obtain the polyetheretherketone.

4. The preparation method according to any one of claims 1-3, characterized in that, The alkali metal is selected from potassium and / or sodium; and / or, the carbonate of the alkali metal is selected from sodium carbonate; and / or, D of the carbonate and / or bicarbonate of the alkali metal 90 ≤ 40 μm; and / or, the molar ratio of the carbonate and / or bicarbonate of the alkali metal to the bisphenol is (1.003 - 1.17):1; and / or, the molar ratio of the organic dihalide to the bisphenol is (1.01 - 1.025):1; and / or, the solvent is an aromatic sulfone, and the aromatic sulfone is selected from at least one of diphenyl sulfone, dibenzothiophene dioxide, phenoxathiin dioxide, and 4-phenylsulfonylbiphenyl; and / or, the organic dihalide is selected from at least one of 4,4'-difluorobenzophenone, 2,4'-difluorobenzophenone, 4-chloro-4'-fluorobenzophenone, 4,4'-dichlorobenzophenone, 1,4-bis(4'-fluorobenzoyl)benzene or a mixture of two or more thereof; and / or, the bisphenol is selected from at least one of hydroquinone, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl ether, 1,4-dihydroxynaphthalene, 2,3-dihydroxynaphthalene or a mixture of two or more thereof; and / or, the organic halide is selected from monofluoro-substituted aromatic halides; 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.

5. The preparation method according to claim 3, characterized in that, In step S2, the reaction conditions include: reducing the pressure to a vacuum gauge pressure of less than -0.01 MPa; the temperature is 115 - 125 °C; and / or, in step S3, the reaction temperature is 250 - 320 °C.

6. The preparation method according to claim 3, wherein In step S4, the end-capping treatment is carried out in the presence of an end-capping agent; and / or, in step S4, the conditions of the end-capping treatment include: the temperature is 295 - 320 °C; the time is 15 - 45 min.

7. The preparation method according to claim 3, characterized in that, In step S5, the cooled reaction product is ground into powder particles; the size of the powder particles is less than 1.3 mm and greater than 0.22 mm.

8. Polyetheretherketone obtained by the preparation method according to any one of claims 1 - 7.

9. The polyetheretherketone according to claim 8, wherein, The polyetheretherketone has at least one of the following properties: 1) The gel content is not more than 0.7%; 2) The melt index is not more than 20 g / 10 min; 3) The polydispersity index (PDI) of the molecular weight distribution is not greater than 2.5; 4) The viscosity is not less than 350 Pa·s; 5) The glass transition temperature (Tg) is at least 143 °C; 6) The melting point (Tm) is at least 330 °C; And / or, the mechanical properties of the polyetheretherketone are as follows: the flexural strength is not less than 140 MPa; And / or, in the chromaticity of the polyetheretherketone, the L value is not less than 70; the a value is not greater than 3; the b value is not greater than 8.

10. Use of the polyetheretherketone polymer according to claim 8 or 9 in aerospace, medical, electronic and electrical appliances, automotive manufacturing, petrochemical industry.

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