A polyether ether ketone resin with very narrow molecular weight distribution and its preparation method and application

Abstract

The present application relates to a kind of extremely narrow molecular weight distribution polyether ether ketone resin and its preparation method and application.The preparation method of polyether ether ketone resin includes the following steps: under inert atmosphere, 4,4'-difluorobenzophenone, phenolic monomer, salt forming agent and solvent are uniformly mixed, gradient temperature is carried out, then end-capped;The gradient temperature includes, initial stage: the temperature holding temperature is 140-210 DEG C, transition stage: the temperature holding temperature is 250-280 DEG C, and final stage: the temperature holding temperature is 300-320 DEG C.The PEEK resin prepared by the present application has very narrow molecular weight distribution, which can significantly improve the chemical, heat stability, fatigue resistance, mechanical properties of PEEK resin, meet the high performance, high quality requirements of PEEK in high-end manufacturing field, such as aerospace, medical, electronic and semiconductor.

Description

Technical Field

[0001] This invention relates to a polyetheretherketone resin with an extremely narrow molecular weight distribution, its preparation method, and its applications. Background Technology

[0002] Polyetheretherketone (PEEK), as a high-performance engineering plastic, possesses excellent comprehensive properties, including heat resistance, abrasion resistance, fatigue resistance, radiation resistance, peel resistance, creep resistance, dimensional stability, impact resistance, chemical resistance, non-toxicity, and flame retardancy. Compared to metallic materials, PEEK has a higher specific strength while being lighter in weight, making it suitable for use as a high-temperature structural material and electrical insulation material. It can be composited with glass fiber or carbon fiber to prepare reinforcing materials, making it suitable for applications in aerospace, automotive, and medical fields where lightweighting is crucial.

[0003] Currently, the domestic synthesis process of PEEK suffers from problems such as low degree of polymerization, poor batch stability, and insufficient green technology, resulting in unstable product performance and high production costs. Depending on the specific operating conditions of different PEEK products, the resin's flowability, processability, stability, and strength will have different requirements and emphases.

[0004] One of the main factors affecting whether PEEK resin performance can meet the requirements of high-end applications is the molecular weight distribution (PDI) of the PEEK resin. Different products require different PDI for different application scenarios, which translates to issues of melt index, flowability, and stability at the material level.

[0005] Molecular weight distribution (PDI) is a core performance parameter that determines the application of PEEK resins / modified materials in various fields. A narrower molecular weight distribution helps to significantly improve the structural uniformity, physicochemical properties, thermodynamic stability, mechanical strength, and processing stability of PEEK resins.

[0006] Therefore, achieving the synthesis and preparation of PEEK resin with narrow molecular weight distribution through polymerization process and technology optimization, and further improving the stability and performance of PEEK products, are urgent problems to be solved in the process of realizing the domestic substitution of PEEK resin and related products. Summary of the Invention

[0007] The technical problem to be solved by the present invention is to overcome the defect of the wide molecular weight distribution of PEEK in the prior art, and to provide a polyether ether ketone resin, its preparation method and application.

[0008] The present invention solves the above-mentioned technical problems through the following technical solution:

[0009] In a first aspect, the present invention provides a method for preparing polyetheretherketone resin, comprising the following steps: subjecting a raw material composition to a gradient temperature increase under an inert atmosphere; and then end-capping; wherein the raw material composition comprises 4,4'-difluorobenzophenone, a phenolic monomer, a salt-forming agent, and a solvent; wherein the temperature of the raw material composition is less than or equal to 100°C, and wherein the raw material composition is in a uniformly mixed state.

[0010] In this invention, the phenolic monomers are conventionally chosen in the art, and preferably are diphenol monomers, such as hydroquinone.

[0011] In this invention, the molar ratio of the phenolic monomer to 4,4'-difluorobenzophenone is preferably such that the reaction can be completed, and more preferably it is (0.87-1.15):1, for example 1:1.

[0012] In this invention, the salt-forming agent is a conventional choice in the art, preferably an alkali metal salt. The alkali metal salt is preferably an alkali metal carbonate, such as sodium carbonate and / or potassium carbonate.

[0013] When the salt-forming agent is an alkali metal carbonate, the molar ratio of the alkali metal carbonate to 4,4'-difluorobenzophenone can be (1-1.5):1, for example, 1.23:1.

[0014] Wherein, when the alkali metal carbonate is sodium carbonate and potassium carbonate, the sodium carbonate may account for more than 90% of the total mass of the alkali metal carbonate. Preferably, the mass ratio of sodium carbonate to potassium carbonate is (10-20):1.

[0015] In this invention, the solvent may be a nitrogen heterocyclic solvent, a sulfone solvent, or an amide solvent.

[0016] The nitrogen-containing heterocyclic solvent may be N-methylpyrrolidone. The sulfone solvent may be selected from one or more of diphenyl sulfone, sulfolane, and dimethyl sulfoxide. The amide solvent may be N,N'-dimethylacetamide.

[0017] In this invention, the solvent may be a solid or a liquid at room temperature.

[0018] Preferably, the solvent has a boiling point of 150°C or higher, more preferably 200°C or higher, and more preferably 300°C or higher.

[0019] In this invention, the solvent does not affect the preparation process of polyetheretherketone resin.

[0020] In this invention, the ratio of the mass of the solvent to the molar mass of 4,4'-difluorobenzophenone is preferably such that the reaction can be completed, and more preferably it is (0.5-1) kg: 1 mol, for example 0.6 kg: 1 mol.

[0021] In this invention, the uniform mixing can be uniform mixing in a solid state or uniform mixing in a solution state.

[0022] When the uniform mixing is a uniform mixing in a solid state, the particle size of the 4,4'-difluorobenzophenone can be 150-300 mesh, preferably 200-300 mesh.

[0023] When the uniform mixing is a uniform mixing in a solid state, the particle size of the phenolic monomer can be 150-300 mesh, preferably 200-300 mesh.

[0024] When the uniform mixing is a uniform mixing in a solid state, the particle size of the phenolic monomer can be 150-300 mesh, preferably 200-300 mesh.

[0025] When the uniform mixing is a uniform mixing in a solid state, the particle size of the salt-forming agent can be 150-300 mesh, preferably 200-300 mesh.

[0026] When the uniform mixing is a uniform mixing in a solid state, the particle size of the solvent can be 150-300 mesh, preferably 200-300 mesh.

[0027] In some specific embodiments of the present invention, the solvent is a high-boiling-point solvent that is solid at room temperature.

[0028] Wherein, when the uniform mixing is a uniform mixing in a solid state, the particle size of the raw material composition can be less than or equal to 200 mesh, preferably 200-300 mesh.

[0029] When the uniform mixing refers to a uniform mixing in a solid state, pre-stirring can be used to achieve this. The pre-stirring time can be 0.5-1 h. The pre-stirring speed is 100-200 rpm. The ambient temperature for pre-stirring can be room temperature, for example, 15-40℃. The pre-stirring atmosphere can be an inert atmosphere. The inert atmosphere can be nitrogen or a rare gas.

[0030] In this invention, the phenolic monomers and the salt-forming agent in the raw material composition hardly react with each other.

[0031] In this invention, the temperature of the raw material composition may be less than or equal to 90°C, preferably less than or equal to 60°C.

[0032] In this invention, the temperature of the raw material composition can be greater than or equal to -20°C, and preferably greater than or equal to 0°C.

[0033] In this invention, the temperature of the raw material composition can be room temperature, for example, 15-40°C.

[0034] In this invention, the inert atmosphere refers to an atmosphere that does not participate in the reaction. Preferably, the gas in the inert atmosphere can be nitrogen or a rare gas.

[0035] In this invention, the environmental pressure for the gradient heating can be atmospheric pressure, such as one standard atmosphere.

[0036] In this invention, the starting temperature of the gradient heating can be less than or equal to 100°C, preferably room temperature, for example, 15-40°C.

[0037] In this invention, the gradient heating may include an initial stage with a holding temperature of 140-210℃, a transition stage with a holding temperature of 250-280℃, and a final stage with a holding temperature of 300-320℃.

[0038] In this invention, the gradient heating can be a three-stage gradient heating, specifically: the initial stage: the holding temperature is 140-210℃, the transition stage: the holding temperature is 250-280℃, and the final stage: the holding temperature is 300-320℃.

[0039] The initial heating time can be 1-4 hours, preferably 1-2 hours, for example, 1 hour or 1.5 hours. The initial holding time can be 0.5-1.5 hours, for example, 1-1.5 hours. The initial ambient pressure can be atmospheric pressure, for example, one standard atmosphere.

[0040] The total time for heating and holding during the transition phase can be 1-8 hours, for example, 4-5 hours. The heating time during the transition phase can be 0.5-1 hour. The holding time during the transition phase can be 0.5-4 hours, for example, 2 hours. The ambient pressure during the transition phase can be atmospheric pressure, for example, one standard atmosphere.

[0041] The total time for heating and holding in the final stage can be 1-8 hours, for example, 4-5 hours. The heating time in the final stage can be 10-30 minutes, for example, 15 minutes or 30 minutes. The holding time in the final stage can be 0.5-1.5 hours, for example, 1 hour. The ambient pressure in the final stage can be atmospheric pressure, for example, one standard atmosphere.

[0042] The final stage of insulation can be at a temperature of 310℃.

[0043] In some specific embodiments of the present invention, the initial stage heat preservation temperature is 140-150°C, and a first intermediate stage is further included between the initial stage and the transition stage, wherein the heat preservation temperature of the first intermediate stage is 190-210°C.

[0044] In some specific embodiments of the present invention, the gradient heating is a four-stage gradient heating, specifically: the initial stage: the holding temperature is 140-150℃, the first intermediate stage: the holding temperature is 190-210℃, the transition stage: the holding temperature is 250-280℃, and the final stage: the holding temperature is 300-320℃.

[0045] The initial heating time can be 0.5-2 hours, for example, 1 hour. The initial holding time can be 0.5-1 hour. The transition heating time can be 10-30 minutes, for example, 15 minutes.

[0046] The heating time in the first intermediate stage can be 0.5-2 hours, for example, 1 hour. The holding time in the first intermediate stage can be 0.5-1 hour. The ambient pressure in the first intermediate stage can be atmospheric pressure, for example, one standard atmosphere.

[0047] In some specific embodiments of the present invention, the heat preservation temperature of the transition stage is 250-255°C, and a second intermediate stage is further included between the transition stage and the final stage, wherein the heat preservation temperature of the second intermediate stage is 275-280°C.

[0048] In some specific embodiments of the present invention, the gradient heating is a four-stage gradient heating, specifically: the initial stage: the holding temperature is 140-210℃, the transition stage: the holding temperature is 250-255℃, the second intermediate stage: the holding temperature is 275-280℃, and the final stage: the holding temperature is 300-320℃.

[0049] The total time for heating and holding during the transition phase can be 0.5-4 hours, for example, 2-2.5 hours. The holding time during the transition phase can be 1.5-2 hours.

[0050] The total heating and holding time in the second intermediate stage can be 0.5-4 hours, for example, 2-2.5 hours. The holding time in the second intermediate stage can be 1.5-2 hours. The heating time in the second intermediate stage can be 10-30 minutes, for example, 15 minutes. The ambient pressure in the second intermediate stage can be atmospheric pressure, for example, one standard atmosphere.

[0051] In certain specific embodiments of the present invention, the gradient heating is a five-stage gradient heating, specifically: initial stage: holding temperature of 140-150℃, first intermediate stage: holding temperature of 190-210℃, transition stage: holding temperature of 250-255℃, second intermediate stage: holding temperature of 275-280℃, and final stage: holding temperature of 300-320℃.

[0052] In this invention, the specific operation of the end-capping can be to add 4,4'-difluorobenzophenone to the reaction system. Preferably, the molar ratio of the 4,4'-difluorobenzophenone added during end-capping to the 4,4'-difluorobenzophenone in step S1 is (0.02-0.05):1.

[0053] In this invention, after end-capping, the reaction product is washed. The washing agent is preferably selected from one or more of acetone, ethanol, and water. The washing time is preferably 4-12 hours. After washing, the product is preferably dried. The drying temperature is preferably 100-120°C.

[0054] Secondly, the present invention provides a polyether ether ketone resin prepared by the method described above.

[0055] Thirdly, the present invention provides a polyetheretherketone resin comprising repeating units as shown in formula (I).

[0056]

[0057] (I)

[0058] The polyether ether ketone resin has a number-average molecular weight (Mn) of 20,000-40,000 and a molecular weight distribution index (PDI) of 1.7-2.6.

[0059] In this invention, the number average molecular weight Mn of the polyether ether ketone resin can be 21,000-36,000, preferably 22,000-30,000, for example 22,056, 22,978, 23,441, 26,491, 26,669 or 27,839.

[0060] In this invention, the molecular weight distribution index (PDI) of the polyether ether ketone resin can be 1.8-2.3, preferably 1.8-2.1, for example 1.83, 2.09, 2.22, 2.26, 2.39, 2.5 or 2.54.

[0061] In this invention, the number-average molecular weight Mn and molecular weight distribution index PDI of the polyether ether ketone resin are obtained by dithioketating the polyether ether ketone resin, obtaining the corresponding data through GPC testing, and then converting the data of the polyether ether ketone resin through monomer molecular weight relationship.

[0062] In this invention, the polyetheretherketone resin, under an air atmosphere and a heating rate of 10°C / min, has a 5% thermal weight loss temperature of not less than 560°C, preferably 560-580°C, such as 560°C, 562°C, 566°C, 567°C, or 569.5°C.

[0063] Fourthly, the present invention provides a raw material composition for polyetheretherketone resin, comprising 4,4'-difluorobenzophenone, phenolic monomers, a salt-forming agent and a solvent; the temperature of the raw material composition is less than or equal to 100°C, and the raw material composition is in a uniformly mixed state.

[0064] In this invention, the phenolic monomers are conventionally chosen in the art, and preferably are diphenol monomers, such as hydroquinone.

[0065] In this invention, the molar ratio of the phenolic monomer to 4,4'-difluorobenzophenone is preferably such that the reaction can be completed, and more preferably it is (0.87-1.15):1, for example 1:1.

[0066] In this invention, the salt-forming agent is a conventional choice in the art, preferably an alkali metal salt. The alkali metal salt is preferably an alkali metal carbonate, such as sodium carbonate and / or potassium carbonate.

[0067] When the salt-forming agent is an alkali metal carbonate, the molar ratio of the alkali metal carbonate to 4,4'-difluorobenzophenone can be (1-1.5):1, for example, 1.23:1.

[0068] Wherein, when the alkali metal carbonate is sodium carbonate and potassium carbonate, the sodium carbonate may account for more than 90% of the total mass of the alkali metal carbonate. Preferably, the mass ratio of sodium carbonate to potassium carbonate is (10-20):1.

[0069] In this invention, the solvent may be a nitrogen heterocyclic solvent, a sulfone solvent, or an amide solvent.

[0070] The nitrogen-containing heterocyclic solvent may be N-methylpyrrolidone. The sulfone solvent may be selected from one or more of diphenyl sulfone, sulfolane, and dimethyl sulfoxide. The amide solvent may be N,N'-dimethylacetamide.

[0071] In this invention, the solvent may be a solid or a liquid at room temperature.

[0072] Preferably, the solvent has a boiling point of 150°C or higher, more preferably 200°C or higher, and more preferably 300°C or higher.

[0073] In this invention, the solvent does not affect the preparation process of polyetheretherketone resin.

[0074] In this invention, the ratio of the mass of the solvent to the molar mass of 4,4'-difluorobenzophenone is preferably such that the reaction can be completed, and more preferably it is (0.5-1) kg: 1 mol, for example 0.6 kg: 1 mol.

[0075] In this invention, the uniform mixing can be uniform mixing in a solid state or uniform mixing in a solution state.

[0076] When the uniform mixing is a uniform mixing in a solid state, the particle size of the 4,4'-difluorobenzophenone can be 150-300 mesh, preferably 200-300 mesh.

[0077] When the uniform mixing is a uniform mixing in a solid state, the particle size of the phenolic monomer can be 150-300 mesh, preferably 200-300 mesh.

[0078] When the uniform mixing is a uniform mixing in a solid state, the particle size of the phenolic monomer can be 150-300 mesh, preferably 200-300 mesh.

[0079] When the uniform mixing is a uniform mixing in a solid state, the particle size of the salt-forming agent can be 150-300 mesh, preferably 200-300 mesh.

[0080] When the uniform mixing is a uniform mixing in a solid state, the particle size of the solvent can be 150-300 mesh, preferably 200-300 mesh.

[0081] In some specific embodiments of the present invention, the solvent is a high-boiling-point solvent that is solid at room temperature.

[0082] Wherein, when the uniform mixing is a uniform mixing in a solid state, the particle size of the raw material composition can be less than or equal to 200 mesh, preferably 200-300 mesh.

[0083] When the uniform mixing refers to a uniform mixing in a solid state, pre-stirring can be used to achieve this. The pre-stirring time can be 0.5-1 h. The pre-stirring speed is 100-200 rpm. The ambient temperature for pre-stirring can be room temperature, for example, 15-40℃. The pre-stirring atmosphere can be an inert atmosphere. The inert atmosphere can be nitrogen or a rare gas.

[0084] In this invention, the phenolic monomers and the salt-forming agent in the raw material composition hardly react with each other.

[0085] In this invention, the temperature of the raw material composition can be room temperature, for example, 15-40°C.

[0086] Fifthly, the present invention provides an application of the polyetheretherketone resin as described above, which is applied in high-end manufacturing fields, such as aerospace, medical, electronic or semiconductor fields.

[0087] Without violating common sense in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0088] The reagents and raw materials used in this invention are all commercially available.

[0089] The positive and progressive effects of this invention are as follows:

[0090] (1) In this invention, the raw material composition of polyether ether ketone resin is in a uniformly mixed state at a lower temperature, which helps the final PEEK resin to have a narrower molecular weight distribution.

[0091] (2) In this invention, the raw material composition of polyether ether ketone resin is mixed evenly at a lower temperature and then the temperature is gradually increased, which helps the final PEEK resin to have a narrower molecular weight distribution.

[0092] (3) In this invention, the obtained PEEK resin has a narrow molecular weight distribution, which will significantly improve the chemical and thermal stability, fatigue resistance and mechanical properties of PEEK resin, and meet the high performance and high quality requirements of PEEK in high-end manufacturing fields such as aerospace, medical, electronics and semiconductor.

[0093] (4) In this invention, polyetheretherketone has a high glass transition temperature, a high melting point and a high crystallization temperature, which is beneficial to the heat resistance stability and strength of the material / product in subsequent applications;

[0094] (5) In this invention, the polyether ether ketone is started at a low temperature during the preparation process and is carried out under normal pressure. There is no risk of high pressure reaction, and the overall production process is safe. Attached Figure Description

[0095] Figure 1 The image shows the infrared spectrum of the polyether ether ketone sample prepared in Example 1-1.

[0096] Figure 2 The molecular weight distribution of the polyether ether ketone sample prepared in Example 1-1 after dithioketalization was measured by gel permeation chromatography (GPC).

[0097] Figure 3 The molecular weight distribution of the polyether ether ketone samples prepared in Examples 1-2 after dithioketation was determined by gel permeation chromatography (GPC).

[0098] Figure 4 The molecular weight distribution of the polyether ether ketone sample prepared in Comparative Example 1-1 after dithioketalization was determined by gel permeation chromatography (GPC).

[0099] Figure 5 The molecular weight distribution of the polyether ether ketone samples prepared in Comparative Examples 1-2 after dithioketation was determined by gel permeation chromatography (GPC).

[0100] Figure 6 The molecular weight distribution of the polyether ether ketone sample prepared in Example 2-1 after dithioketation was determined by gel permeation chromatography (GPC).

[0101] Figure 7 The molecular weight distribution of the polyether ether ketone sample prepared in Example 2-2 after dithioketalization was measured by gel permeation chromatography (GPC).

[0102] Figure 8 The molecular weight distribution of the polyether ether ketone sample prepared in Comparative Example 2-1 after dithioketalization was determined by gel permeation chromatography (GPC).

[0103] Figure 9 The molecular weight distribution of the polyether ether ketone sample prepared in Example 3-1 after dithioketalization was measured by gel permeation chromatography (GPC).

[0104] Figure 10 The molecular weight distribution of the polyether ether ketone sample prepared in Example 3-2 after dithioketalization was measured by gel permeation chromatography (GPC).

[0105] Figure 11 The molecular weight distribution of the polyether ether ketone sample prepared in Comparative Example 3-1 after dithioketalization was determined by gel permeation chromatography (GPC). Detailed Implementation

[0106] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below in conjunction with embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of this invention and should not be construed as limiting the scope of protection of this invention. All technologies implemented based on the above content of this invention are covered within the scope of protection intended by this invention.

[0107] In the following examples and comparative examples, the particle size of the main raw materials (4,4'-difluorobenzophenone, hydroquinone, diphenyl sulfone and sodium carbonate) was 150-300 mesh.

[0108] Example 1: The salt-forming agent is pure Na2CO3

[0109] Example 1-1

[0110] A polyetheretherketone resin and its preparation method are as follows:

[0111] A four-port split 3000 mL reactor is equipped with a heating jacket, a top-mounted stirrer, a three-way mercury thermometer (maximum measurement value 400℃), a water separator, and a condenser to construct the reaction apparatus. A nitrogen gas flow of 3 L / min is stably introduced through the inlet of the three-way mercury thermometer.

[0112] 436.4 g (2 mol) of 4,4'-difluorobenzophenone, 220.2 g (2 mol) of hydroquinone, 1.2 kg (5.5 mol) of diphenyl sulfone and 259.68 g (2.45 mol) of sodium carbonate in powder form were added to the reactor, and the agitator was started at 100 rpm to stir the material thoroughly for 1 h until the particle size of the material was less than 200 mesh. During this period, a nitrogen gas flow was maintained to ensure sufficient gas replacement.

[0113] Under normal pressure, the reactor was uniformly heated from room temperature to 140°C for 1 hour and held at that temperature for 30 minutes; then uniformly heated to 210°C for 1 hour and held at that temperature for 1 hour; after 15 minutes, the temperature was further increased to 250°C and held at that temperature for 2 hours; after 15 minutes, the temperature was increased to 280°C and held at that temperature for 2 hours; finally, after 15 minutes, the temperature was increased to 310°C and held at that temperature for 1 hour. Finally, 5 g of 4,4'-difluorobenzophenone was added to the reaction system to seal the reaction and complete the reaction.

[0114] After the reaction was complete, the material was poured into a stainless steel pan, cooled and solidified, then pulverized. 100 g of the sample was placed in a Soxhlet extractor and washed with acetone, ethanol, and water for 12 h each. The sample was then dried at 120°C overnight to obtain pure PEEK resin. Its infrared spectrum is shown below. Figure 1 .

[0115] Examples 1-2

[0116] A polyetheretherketone resin and its preparation method are as follows:

[0117] A four-port split 3000 mL reactor is equipped with a heating jacket, a top-mounted stirrer, a three-way mercury thermometer (maximum measurement value 400℃), a water separator, and a condenser to construct the reaction apparatus. A nitrogen gas flow of 3 L / min is stably introduced through the inlet of the three-way mercury thermometer.

[0118] 436.4 g (2 mol) of 4,4'-difluorobenzophenone, 220.2 g (2 mol) of hydroquinone, 1.2 kg (5.5 mol) of diphenyl sulfone and 259.68 g (2.45 mol) of sodium carbonate in powder form were added to the reactor, and the agitator was started at 100 rpm to stir the material thoroughly for 1 h until the particle size of the material was less than 200 mesh. During this period, a nitrogen gas flow was maintained to ensure sufficient gas replacement.

[0119] Under normal pressure, the reactor was uniformly heated from room temperature to 140°C for 1 hour and held at that temperature for 1.5 hours; then, after 30 minutes, the temperature was further increased to 250°C and held for 4 hours; finally, after 30 minutes, the temperature was increased to 310°C and held for 1 hour. Finally, 5 g of 4,4'-difluorobenzophenone was added to the reaction system to seal the reaction and complete the reaction.

[0120] After the reaction was complete, the material was poured into a stainless steel pan, cooled and solidified, then crushed. 100 g of the sample was placed in a Soxhlet extractor and washed with acetone, ethanol and water for 12 h, respectively. The sample was then dried at 120 °C overnight to obtain the PEEK resin sample.

[0121] Comparative Example 1-1

[0122] A polyetheretherketone resin and its preparation method are as follows:

[0123] A four-port split 3000 mL reactor is equipped with a heating jacket, a top-mounted stirrer, a three-way mercury thermometer (maximum measurement value 400℃), a water separator, and a condenser to construct the reaction apparatus. A nitrogen gas flow of 3 L / min is stably introduced through the inlet of the three-way mercury thermometer.

[0124] Add 436.4 g (2 mol) of 4,4'-difluorobenzophenone, 220.2 g (2 mol) of hydroquinone, 1.2 kg (5.5 mol) of diphenyl sulfone and 259.68 g (2.45 mol) of sodium carbonate to the reactor in sequence without stirring; during this period, maintain a nitrogen flow to ensure sufficient gas replacement.

[0125] Under normal pressure, the reactor was uniformly heated from room temperature to 140°C for 1 hour and held at that temperature for 30 minutes; then uniformly heated to 210°C for 1 hour and held at that temperature for 1 hour; after 15 minutes, the temperature was further increased to 250°C and held at that temperature for 2 hours; after 15 minutes, the temperature was increased to 280°C and held at that temperature for 2 hours; finally, after 15 minutes, the temperature was increased to 310°C and held at that temperature for 1 hour. Finally, 5 g of 4,4'-difluorobenzophenone was added to the reaction system to seal the reaction and complete the reaction.

[0126] After the reaction was complete, the material was poured into a stainless steel pan, cooled and solidified, then crushed. 100 g of the sample was placed in a Soxhlet extractor and washed with acetone, ethanol and water for 12 h, respectively. The sample was then dried at 120 °C overnight to obtain the PEEK resin sample.

[0127] Comparative Examples 1-2

[0128] A polyetheretherketone resin and its preparation method are as follows:

[0129] A four-port split 3000 mL reactor is equipped with a heating jacket, a top-mounted stirrer, a three-way mercury thermometer (maximum measurement value 400℃), a water separator, and a condenser to construct the reaction apparatus. A nitrogen gas flow of 3 L / min is stably introduced through the inlet of the three-way mercury thermometer.

[0130] Add 436.4 g (2 mol) of 4,4'-difluorobenzophenone, 220.2 g (2 mol) of hydroquinone, 1.2 kg (5.5 mol) of diphenyl sulfone and 259.68 g (2.45 mol) of sodium carbonate to the reactor in sequence without stirring; during this period, maintain a nitrogen flow to ensure sufficient gas replacement.

[0131] Under normal pressure, the reactor was uniformly heated from room temperature to 140°C for 1 hour and held at that temperature for 1.5 hours; then, after 30 minutes, the temperature was further increased to 250°C and held for 4 hours; finally, after 30 minutes, the temperature was increased to 310°C and held for 1 hour. Finally, 5 g of 4,4'-difluorobenzophenone was added to the reaction system to seal the reaction and complete the reaction.

[0132] After the reaction was complete, the material was poured into a stainless steel pan, cooled and solidified, then crushed. 100 g of the sample was placed in a Soxhlet extractor and washed with acetone, ethanol and water for 12 h, respectively. The sample was then dried at 120 °C overnight to obtain the PEEK resin sample.

[0133] Example 2: Salt-forming agents of Na₂CO₃ and K₂CO₃ in a ratio of 20:1

[0134] Example 2-1

[0135] A polyetheretherketone resin and its preparation method are as follows:

[0136] A four-port split 3000 mL reactor is equipped with a heating jacket, a top-mounted stirrer, a three-way mercury thermometer (maximum measurement value 400℃), a water separator, and a condenser to construct the reaction apparatus. A nitrogen gas flow of 3 L / min is stably introduced through the inlet of the three-way mercury thermometer.

[0137] 436.4 g (2 mol) of 4,4'-difluorobenzophenone, 220.2 g (2 mol) of hydroquinone, 1.2 kg (5.5 mol) of diphenyl sulfone, 246.72 g (2.33 mol) of sodium carbonate and 16.56 g (0.12 mol) of potassium carbonate in powder form were added to the reactor. The agitator was started at 100 rpm and the materials were stirred thoroughly for 1 h until the particle size of the materials was less than 200 mesh. During this period, a nitrogen gas flow was maintained to ensure sufficient gas replacement.

[0138] Under normal pressure, the reactor was uniformly heated from room temperature to 140°C for 1 hour and held at that temperature for 30 minutes; then uniformly heated to 210°C for 1 hour and held at that temperature for 1 hour; after 15 minutes, the temperature was further increased to 250°C and held at that temperature for 2 hours; after 15 minutes, the temperature was increased to 280°C and held at that temperature for 2 hours; finally, after 15 minutes, the temperature was increased to 310°C and held at that temperature for 1 hour. Finally, 5 g of 4,4'-difluorobenzophenone was added to the reaction system to seal the reaction and complete the reaction.

[0139] After the reaction was complete, the material was poured into a stainless steel pan, cooled and solidified, then crushed. 100 g of the sample was placed in a Soxhlet extractor and washed with acetone, ethanol and water for 12 h respectively. The sample was then dried at 120 °C overnight to obtain a pure PEEK resin sample.

[0140] Example 2-2

[0141] A polyetheretherketone resin and its preparation method are as follows:

[0142] A four-port split 3000 mL reactor is equipped with a heating jacket, a top-mounted stirrer, a three-way mercury thermometer (maximum measurement value 400℃), a water separator, and a condenser to construct the reaction apparatus. A nitrogen gas flow of 3 L / min is stably introduced through the inlet of the three-way mercury thermometer.

[0143] 436.4 g (2 mol) of 4,4'-difluorobenzophenone, 220.2 g (2 mol) of hydroquinone, 1.2 kg (5.5 mol) of diphenyl sulfone, 246.72 g (2.33 mol) of sodium carbonate and 16.56 g (0.12 mol) of potassium carbonate in powder form were added to the reactor. The agitator was started at 100 rpm and the materials were stirred thoroughly for 1 h until the particle size of the materials was less than 200 mesh. During this period, a nitrogen gas flow was maintained to ensure sufficient gas replacement.

[0144] Under normal pressure, the reactor was uniformly heated from room temperature to 140°C for 1 hour and held at that temperature for 1.5 hours; then, after 30 minutes, the temperature was further increased to 250°C and held for 4 hours; finally, after 30 minutes, the temperature was increased to 310°C and held for 1 hour. Finally, 5 g of 4,4'-difluorobenzophenone was added to the reaction system to seal the reaction and complete the reaction.

[0145] After the reaction was complete, the material was poured into a stainless steel pan, cooled and solidified, then crushed. 100 g of the sample was placed in a Soxhlet extractor and washed with acetone, ethanol and water for 12 h, respectively. The sample was then dried at 120 °C overnight to obtain the PEEK resin sample.

[0146] Comparative Example 2-1

[0147] A polyetheretherketone resin and its preparation method are as follows:

[0148] A four-port split 3000 mL reactor is equipped with a heating jacket, a top-mounted stirrer, a three-way mercury thermometer (maximum measurement value 400℃), a water separator, and a condenser to construct the reaction apparatus. A nitrogen gas flow of 3 L / min is stably introduced through the inlet of the three-way mercury thermometer.

[0149] Add 436.4 g (2 mol) of 4,4'-difluorobenzophenone, 220.2 g (2 mol) of hydroquinone, 1.2 kg (5.5 mol) of diphenyl sulfone, 246.72 g (2.33 mol) of sodium carbonate and 16.56 g (0.12 mol) of potassium carbonate to the reactor in sequence without stirring; during this period, maintain a nitrogen gas flow to ensure sufficient gas replacement.

[0150] Under normal pressure, the reactor was uniformly heated from room temperature to 140°C for 1 hour and held at that temperature for 30 minutes; then uniformly heated to 210°C for 1 hour and held at that temperature for 1 hour; after 15 minutes, the temperature was further increased to 250°C and held at that temperature for 2 hours; after 15 minutes, the temperature was increased to 280°C and held at that temperature for 2 hours; finally, after 15 minutes, the temperature was increased to 310°C and held at that temperature for 1 hour. Finally, 5 g of 4,4'-difluorobenzophenone was added to the reaction system to seal the reaction and complete the reaction.

[0151] After the reaction was complete, the material was poured into a stainless steel pan, cooled and solidified, then crushed. 100 g of the sample was placed in a Soxhlet extractor and washed with acetone, ethanol and water for 12 h, respectively. The sample was then dried at 120 °C overnight to obtain the PEEK resin sample.

[0152] Example 3: Na₂CO₃ and K₂CO₃ with a salt-forming agent ratio of 10:1

[0153] Example 3-1

[0154] A polyetheretherketone resin and its preparation method are as follows:

[0155] A four-port split 3000 mL reactor is equipped with a heating jacket, a top-mounted stirrer, a three-way mercury thermometer (maximum measurement value 400℃), a water separator, and a condenser to construct the reaction apparatus. A nitrogen gas flow of 3 L / min is stably introduced through the inlet of the three-way mercury thermometer.

[0156] 436.4 g (2 mol) of 4,4'-difluorobenzophenone, 220.2 g (2 mol) of hydroquinone, 1.2 kg (5.5 mol) of diphenyl sulfone, 236.07 g (2.23 mol) of sodium carbonate and 30.78 g (0.22 mol) of potassium carbonate in powder form were added to the reactor. The agitator was started at 100 rpm and the materials were stirred thoroughly for 1 h until the particle size of the materials was less than 200 mesh. During this period, a nitrogen gas flow was maintained to ensure sufficient gas replacement.

[0157] Under normal pressure, the reactor was uniformly heated from room temperature to 140°C for 1 hour and held at that temperature for 30 minutes; then uniformly heated to 210°C for 1 hour and held at that temperature for 1 hour; after 15 minutes, the temperature was further increased to 250°C and held at that temperature for 2 hours; after 15 minutes, the temperature was increased to 280°C and held at that temperature for 2 hours; finally, after 15 minutes, the temperature was increased to 310°C and held at that temperature for 1 hour. Finally, 5 g of 4,4'-difluorobenzophenone was added to the reaction system to seal the reaction and complete the reaction.

[0158] After the reaction was complete, the material was poured into a stainless steel pan, cooled and solidified, then crushed. 100 g of the sample was placed in a Soxhlet extractor and washed with acetone, ethanol and water for 12 h respectively. The sample was then dried at 120 °C overnight to obtain a pure PEEK resin sample.

[0159] Example 3-2

[0160] A polyetheretherketone resin and its preparation method are as follows:

[0161] A four-port split 3000 mL reactor is equipped with a heating jacket, a top-mounted stirrer, a three-way mercury thermometer (maximum measurement value 400℃), a water separator, and a condenser to construct the reaction apparatus. A nitrogen gas flow of 3 L / min is stably introduced through the inlet of the three-way mercury thermometer.

[0162] 436.4 g (2 mol) of 4,4'-difluorobenzophenone, 220.2 g (2 mol) of hydroquinone, 1.2 kg (5.5 mol) of diphenyl sulfone, 236.07 g (2.23 mol) of sodium carbonate and 30.78 g (0.22 mol) of potassium carbonate in powder form were added to the reactor. The agitator was started at 100 rpm and the materials were stirred thoroughly for 1 h until the particle size of the materials was less than 200 mesh. During this period, a nitrogen gas flow was maintained to ensure sufficient gas replacement.

[0163] Under normal pressure, the reactor was uniformly heated from room temperature to 140°C for 1 hour and held at that temperature for 1.5 hours; then, after 30 minutes, the temperature was further increased to 250°C and held for 4 hours; finally, after 30 minutes, the temperature was increased to 310°C and held for 1 hour. Finally, 5 g of 4,4'-difluorobenzophenone was added to the reaction system to seal the reaction and complete the reaction.

[0164] After the reaction was complete, the material was poured into a stainless steel pan, cooled and solidified, then crushed. 100 g of the sample was placed in a Soxhlet extractor and washed with acetone, ethanol and water for 12 h, respectively. The sample was then dried at 120 °C overnight to obtain the PEEK resin sample.

[0165] Comparative Example 3-1

[0166] A polyetheretherketone resin and its preparation method are as follows:

[0167] A four-port split 3000 mL reactor is equipped with a heating jacket, a top-mounted stirrer, a three-way mercury thermometer (maximum measurement value 400℃), a water separator, and a condenser to construct the reaction apparatus. A nitrogen gas flow of 3 L / min is stably introduced through the inlet of the three-way mercury thermometer.

[0168] Add 436.4 g (2 mol) of 4,4'-difluorobenzophenone, 220.2 g (2 mol) of hydroquinone, 1.2 kg (5.5 mol) of diphenyl sulfone, 236.07 g (2.23 mol) of sodium carbonate and 30.78 g (0.22 mol) of potassium carbonate to the reactor in sequence without stirring; during this period, maintain a nitrogen gas flow to ensure sufficient gas replacement.

[0169] Under normal pressure, the reactor was uniformly heated from room temperature to 140°C for 1 hour and held at that temperature for 30 minutes; then uniformly heated to 210°C for 1 hour and held at that temperature for 1 hour; after 15 minutes, the temperature was further increased to 250°C and held at that temperature for 2 hours; after 15 minutes, the temperature was increased to 280°C and held at that temperature for 2 hours; finally, after 15 minutes, the temperature was increased to 310°C and held at that temperature for 1 hour. Finally, 5 g of 4,4'-difluorobenzophenone was added to the reaction system to seal the reaction and complete the reaction.

[0170] After the reaction was complete, the material was poured into a stainless steel pan, cooled and solidified, then crushed. 100 g of the sample was placed in a Soxhlet extractor and washed with acetone, ethanol and water for 12 h, respectively. The sample was then dried at 120 °C overnight to obtain the PEEK resin sample.

[0171] The main experimental conditions for each embodiment and comparative example are listed below.

[0172]

[0173] Example 1: Molecular weight and molecular weight distribution of PEEK resin

[0174] 1. Test subject: PEEK resin of all examples and comparative examples.

[0175] 2. Test Method: The obtained PEEK resin sample was dithioketated and the molecular weight and molecular weight distribution of the treated sample were obtained by GPC testing. Then, the molecular weight and molecular weight distribution of the prepared pure PEEK resin sample were obtained by converting the monomer molecular weight relationship. The specific steps are as follows:

[0176] Add 480 mL of dichloromethane to a three-necked flask equipped with a mechanical stirrer, nitrogen protection, and reflux device. Then add 28.8 g of PEEK resin in batches. After dispersing evenly, add 120 mL of trifluoroacetic acid to fully dissolve the PEEK, resulting in a yellow viscous solution.

[0177] Next, 10.96 mL of 1,2-ethylenedithiol and 31.56 mL of boron trifluoride diethyl ether were added to the solution sequentially. During this process, the viscosity of the solution gradually decreased and turned dark red. After reacting at room temperature for 24 hours, the polymer solution was poured into a large amount of ethanol to obtain the crude product. The product was mechanically pulverized and repeatedly refluxed with ethanol until no obvious 1,2-ethylenedithiol odor was detected. Finally, the product was vacuum dried at 60°C for 8 hours to obtain a white solid.

[0178] By converting crystalline PEEK into dithioacetate, making it soluble in common organic solvents, it is easier to characterize using Shimadzu LC-40 gel permeation chromatography (GPC). This conversion reaction is reversible and has no degradation or cross-linking side reactions. Therefore, the molecular weight and molecular weight distribution of the tested PEEK resin can be obtained by converting the molecular weight obtained through GPC (mobile phase THF, flow rate 1 ml / min, column temperature 40℃).

[0179] 3. Test Results: The polyetheretherketone samples after dithioketation treatment, as measured by gel permeation chromatography (GPC), are shown below. Figures 2 to 11 The specific results will be provided later.

[0180] Example 2: Thermal stability of PEEK resin

[0181] 1. Test subject: PEEK resin of all examples and comparative examples.

[0182] 2. Test method: Place the PEEK resin in a thermogravimetric analyzer (TGA) under air atmosphere, and record the temperature at which the sample loses 5% of its mass at a heating rate of 10℃ / min.

[0183] 3. Test results: see below.

[0184] Example 3: Heat resistance and strength of PEEK resin

[0185] 1. Test subject: PEEK resin of all examples and comparative examples.

[0186] 2. Test Methods: The glass transition temperature, higher melting point, and higher crystallization temperature were tested using methods generally accepted in the field. Glass transition temperature Tglass transition temperature g Melting point (T) refers to the temperature at which the amorphous portion of an amorphous (non-crystalline) polymer transitions from a glassy state to a rubbery state. m Crystallization temperature (T) refers to the temperature at which the crystal structure of a crystalline polymer completely disintegrates when heated, transforming from an ordered three-dimensional crystalline state to a disordered viscous flow state. c This refers to the temperature at which a polymer transforms from an amorphous or elastic state to a crystalline state during the cooling process.

[0187] 3. Test results: See the table below.

[0188]

[0189] Comparing Example 1-1 with Comparative Example 1-1, it can be seen that in Example 1-1, the raw materials were premixed to a uniform state at room temperature, and the resulting PEEK resin had a narrower molecular weight distribution and higher thermal stability.

[0190] Thermogravimetric analysis and glass transition temperature tests show that the embodiment also achieved higher thermal stability; and the higher crystallization temperature indicates that the material of the embodiment can have better thermal stability and strength properties in subsequent material / product applications.

[0191] A comparison of Examples 1-1 and 1-2 shows that using a more precise temperature gradient also helps to obtain PEEK resin with a narrower molecular weight distribution. Similarly, the same conclusion can be drawn from a comparison of Examples 2 and 3.

[0192] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No reference numerals in the claims should be construed as limiting the scope of the claims.

[0193] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A method for preparing polyetheretherketone resin, characterized in that, It includes the following steps: Under an inert atmosphere, the raw material composition is subjected to a gradient temperature increase; then it is end-capped; the raw material composition includes 4,4'-difluorobenzophenone, phenolic monomers, salt-forming agents and solvents; the temperature of the raw material composition is less than or equal to 100°C, and the raw material composition is in a uniformly mixed state; the uniform mixing is either a solid state uniform mixing or a solution state uniform mixing; when the uniform mixing is a solid state uniform mixing, it is achieved by pre-stirring.

2. The method for preparing polyetheretherketone resin according to claim 1, characterized in that, The temperature of the raw material composition is room temperature.

3. The method for preparing polyetheretherketone resin according to claim 1, characterized in that, The temperature of the raw material composition is 15-40℃.

4. The method for preparing polyetheretherketone resin according to claim 1, characterized in that, The uniform mixing is a uniform mixing in a solid state, and the particle size of the raw material composition is less than or equal to 200 mesh.

5. The method for preparing polyetheretherketone resin according to claim 1, characterized in that, The uniform mixing is a uniform mixing in a solid state, and the particle size of the raw material composition is 200-300 mesh.

6. The method for preparing polyetheretherketone resin according to claim 1, characterized in that, The starting temperature for the gradient heating is room temperature.

7. The method for preparing polyetheretherketone resin according to claim 1, characterized in that, The starting temperature for the gradient heating is 15-40℃.

8. The method for preparing polyetheretherketone resin according to claim 1, characterized in that, It satisfies at least one of the following conditions: (1) The phenolic monomers are diphenol monomers; (2) The molar ratio of the phenolic monomer to 4,4'-difluorobenzophenone is (0.87-1.15):1; (3) The salt-forming agent is an alkali metal salt; (4) The solvent is a nitrogen heterocyclic solvent, a sulfone solvent, or an amide solvent; (5) The boiling point of the solvent is greater than or equal to 150°C; (6) The ratio of the mass of the solvent to the molar mass of 4,4'-difluorobenzophenone is (0.5-1) kg: 1 mol; (7) The temperature of the raw material composition is less than or equal to 90°C; (8) The temperature of the raw material composition is greater than or equal to -20°C.

9. The method for preparing polyetheretherketone resin according to claim 8, characterized in that, It satisfies at least one of the following conditions: (1) The phenolic monomer is hydroquinone; (2) The molar ratio of the phenolic monomer to 4,4'-difluorobenzophenone is 1:1; (3) The salt-forming agent is an alkali metal carbonate; (4) The boiling point of the solvent is greater than or equal to 200℃; (5) The ratio of the mass of the solvent to the molar mass of 4,4'-difluorobenzophenone is 0.6 kg: 1 mol; (6) The temperature of the raw material composition is less than or equal to 60°C; (7) The temperature of the raw material composition is greater than or equal to 0°C.

10. The method for preparing polyetheretherketone resin according to claim 9, characterized in that, It satisfies at least one of the following conditions: (1) The salt-forming agent is sodium carbonate and / or potassium carbonate; (2) The boiling point of the solvent is greater than or equal to 300℃.

11. The method for preparing polyetheretherketone resin according to claim 9, characterized in that, It satisfies at least one of the following conditions: (1) The alkali metal carbonate is sodium carbonate and potassium carbonate, wherein the sodium carbonate accounts for more than 90% of the total mass of the alkali metal carbonate; (2) The molar ratio of the alkali metal carbonate to 4,4'-difluorobenzophenone is (1-1.5):1; (3) The nitrogen-containing heterocyclic solvent is N-methylpyrrolidone; (4) The sulfone solvent is selected from one or more of diphenyl sulfone, sulfolane cyclobutane, and dimethyl sulfoxide; (5) The amide solvent is N,N'-dimethylacetamide.

12. The method for preparing polyetheretherketone resin according to claim 11, characterized in that, It satisfies at least one of the following conditions: (1) The mass ratio of sodium carbonate to potassium carbonate is (10-20): 1; (2) The molar ratio of the alkali metal carbonate to 4,4'-difluorobenzophenone is 1.23:1; (3) The nitrogen heterocyclic solvent is N-methylpyrrolidone.

13. The method for preparing polyetheretherketone resin according to claim 1, characterized in that, It satisfies at least one of the following conditions: (1) The gas in the inert atmosphere is nitrogen or a rare gas; (2) The ambient pressure for the gradient heating is atmospheric pressure; (3) The starting temperature of the gradient heating is less than or equal to 100℃; (4) The gradient heating includes the following stages: initial stage: heat preservation temperature of 140-210℃, transition stage: heat preservation temperature of 250-280℃, and final stage: heat preservation temperature of 300-320℃. (5) The specific operation of the end capping is to add 4,4'-difluorobenzophenone to the reaction system; (6) After the end capping, the reaction product is washed.

14. The method for preparing polyetheretherketone resin according to claim 13, characterized in that, It satisfies at least one of the following conditions: (1) The ambient pressure for the gradient heating is one standard atmosphere; (2) The molar ratio of 4,4'-difluorobenzophenone added during the end-capping process to that in step S1 is (0.02-0.05): 1; (3) The detergent used for washing is selected from one or more of acetone, ethanol and water.

15. The method for preparing polyetheretherketone resin according to claim 14, characterized in that, It satisfies at least one of the following conditions: (1) The washing time is 4-12 h; (2) The washing process is followed by drying.

16. The method for preparing polyetheretherketone resin according to claim 15, characterized in that, The drying temperature is 100-120℃.

17. The method for preparing polyetheretherketone resin according to claim 13, characterized in that, It satisfies at least one of the following conditions: (1) The initial heating time is 1-4 h; (2) The initial heat preservation time is 0.5-1.5 h; (3) The environmental pressure in the initial stage is atmospheric pressure; (4) The total time for heating and heat preservation during the transition phase is 1-8 h; (5) The heating time during the transition phase is 0.5-1 h; (6) The heat preservation time during the transition stage is 0.5-4 h; (7) The environmental pressure during the transition phase is atmospheric pressure; (8) The total time for heating and holding in the final stage is 1-8 h; (9) The heating time for the final stage is 10-30 min; (10) The heat preservation time in the final stage is 0.5-1.5 h; (11) The environmental pressure of the final stage is atmospheric pressure.

18. The method for preparing polyetheretherketone resin according to claim 17, characterized in that, It satisfies at least one of the following conditions: (1) The initial heating time is 1-2 h; (2) The initial heat preservation time is 1-1.5 h; (3) The environmental pressure in the initial stage is one standard atmosphere; (4) The total time for heating and heat preservation during the transition phase is 4-5 hours; (5) The heat preservation time during the transition phase is 2 hours; (6) The environmental pressure during the transition phase is one standard atmosphere; (7) The total time for heating and holding in the final stage is 4-5 hours; (8) The heating time for the final stage is 15 min or 30 min; (9) The heat preservation time for the final stage is 1 hour; (10) The environmental pressure of the final stage is one standard atmosphere.

19. The method for preparing polyetheretherketone resin according to claim 13, characterized in that, It satisfies at least one of the following conditions: (1) The initial stage heat preservation temperature is 140-150℃, and the initial stage and the transition stage further include a first intermediate stage, the heat preservation temperature of the first intermediate stage is 190-210℃. (2) The heat preservation temperature of the transition stage is 250-255℃, and a second intermediate stage is included between the transition stage and the final stage, wherein the heat preservation temperature of the second intermediate stage is 275-280℃. (3) The final stage of heat preservation temperature is 310℃.

20. The method for preparing polyetheretherketone resin according to claim 19, characterized in that, It satisfies at least one of the following conditions: (1) The initial heating time is 0.5-2 h; (2) The initial heat preservation time is 0.5-1 h; (3) The heating time of the first intermediate stage is 0.5-2 h; (4) The heat preservation time of the first intermediate stage is 0.5-1 h; (5) The environmental pressure of the first intermediate stage is atmospheric pressure; (6) The heating time during the transition phase is 10-30 min; (7) The total time for heating and holding during the transition phase is 0.5-4 h; (8) The heat preservation time during the transition stage is 1.5-2 h; (9) The total time for heating and holding in the second intermediate stage is 0.5-4 h; (10) The heat preservation time for the second intermediate stage is 1.5-2 h; (11) The heating time for the second intermediate stage is 10-30 min; (12) The environmental pressure of the second intermediate stage is normal pressure.

21. The method for preparing polyetheretherketone resin according to claim 20, characterized in that, It satisfies at least one of the following conditions: (1) The initial heating time is 1 h; (2) The heating time of the first intermediate stage is 1 h; (3) The environmental pressure of the first intermediate stage is one standard atmosphere; (4) The heating time for the transition phase is 15 min; (5) The total time for heating and holding during the transition phase is 2-2.5 h; (6) The total time for heating and holding in the second intermediate stage is 2-2.5 h; (7) The heating time for the second intermediate stage is 15 min; (8) The environmental pressure of the second intermediate stage is one standard atmosphere.

22. A polyetheretherketone resin prepared by the method of any one of claims 1-21.

23. The polyetheretherketone resin according to claim 22, characterized in that, It contains repeating units as shown in equation (I), ； (I)； The polyether ether ketone resin has a number-average molecular weight (Mn) of 20,000-40,000 and a molecular weight distribution index (PDI) of 1.7-2.

6.

24. The polyetheretherketone resin according to claim 23, characterized in that, It satisfies at least one of the following conditions: (1) The number average molecular weight Mn of the polyether ether ketone resin is 21,000-36,000; (2) The molecular weight distribution index (PDI) of the polyether ether ketone resin is 1.8-2.

3.

25. The polyetheretherketone resin according to claim 24, characterized in that, It satisfies at least one of the following conditions: (1) The number average molecular weight Mn of the polyether ether ketone resin is 22,000-30,000; (2) The molecular weight distribution index (PDI) of the polyether ether ketone resin is 1.8-2.

1.

26. An application of the polyetheretherketone resin as described in any one of claims 22-25, characterized in that, It is applied in the field of high-end manufacturing, namely aviation, aerospace, medical, electronics or semiconductor.

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