A process for the preparation of polyaryletherketones and the polyaryletherketones obtained

Abstract

The application relates to a method for preparing a polyaryletherketone and the obtained polyaryletherketone, belonging to the field of biological medicine industry, comprising: a) laying part of solid aromatic sulfone solvent in a reactor to cover the bottom and part of the inner wall of the reactor; b) adding reactants and optionally a catalyst, wherein the reactants comprise a dihalodiphenyl ketone and a diphenol monomer, and the catalyst is an alkali metal carbonate; c) laying the remaining solid aromatic sulfone solvent on the obtained reactant in step b) to completely cover the reactant with the aromatic sulfone solvent; d) under an inert atmosphere, carrying out nucleophilic polycondensation of the dihalodiphenyl ketone and the diphenol monomer to obtain the polyaryletherketone; wherein the weight ratio of the solid aromatic sulfone solvent used in step a) to the remaining solid aromatic sulfone solvent in step c) is in the range of 2:1 to 3.5:1; and wherein the molar ratio of the dihalodiphenyl ketone to the diphenol monomer is in the range of 1.001-1.04:1.

Description

Technical Field

[0001] This application belongs to the field of biopharmaceutical industry and relates to polyaryletherketones, more specifically to a method for preparing polyaryletherketones and the resulting polyaryletherketones. Background Technology

[0002] Polyaryletherketone (PAEK) is a class of high-performance specialty engineering plastics with aromatic rings as a rigid backbone and ether bonds (-O-) and ketone groups (-CO-) as connecting groups. Its molecular chain repeats the alternating structure of "aromatic ring-ether bond-ketone group". This structure endows the material with a series of outstanding properties such as high temperature resistance, chemical corrosion resistance, high mechanical strength, good flame retardancy, and excellent biocompatibility. It is one of the most widely used and technologically mature categories of specialty engineering plastics in the world.

[0003] Specifically, polyetheretherketone (PEEK) is a polyaryletherketone first developed and commercialized by ICI in the UK in the late 1970s, and put into industrial production in 1987. This material not only plays a key role in important industries such as aerospace, automotive manufacturing, medical implants, and electronics, but also, due to its outstanding mechanical strength, good chemical stability, and excellent high-temperature resistance, has become one of the preferred materials to replace metals and traditional engineering plastics.

[0004] Currently, the synthesis methods for polyetheretherketone (PEEK) include electrophilic substitution and nucleophilic substitution. Electrophilic substitution typically uses diphenyl ether and terephthaloyl chloride as monomers, undergoing a Friedel-Crafts acylation reaction catalyzed by a Lewis acid at low temperatures. This route is simple, but involves numerous side reactions and is difficult to obtain products with extremely high molecular weights. Nucleophilic substitution typically involves a high-temperature nucleophilic substitution condensation reaction of dihalobenzophenone with aromatic bisphenol monomers such as hydroquinone in a polar solvent using a base as a catalyst. This route is technologically mature and is the main method for industrial production of PEEK.

[0005] However, due to limitations in the feeding method, the components in the reaction system (solvent, dihalobenzophenone, and bisphenol monomers) remain solid when added to the reactor until heated to above 100°C, causing the solvent and dihalobenzophenone to melt. The remaining reactants dissolve in the solvent, forming a homogeneous liquid mixture, which then reacts at a higher temperature. This conventional feeding method easily leads to uneven temperature distribution within the reactor when heating the solid mixture, resulting in localized overheating or low heat transfer efficiency. If the solvent is added first, it often melts and accumulates at the bottom of the reactor, while the upper reactants solidify into hard lumps after the dihalobenzophenone melts, preventing contact with the solvent. If the reactants are added first, they may remain unmelted for a long time, resulting in slow solid-state heat transfer and localized overheating, with the bottom reactants charring. These problems severely affect the efficiency of the polymerization reaction and the accuracy of the experiment. Therefore, improvements are needed in the preparation method of polyaryletherketones, especially the feeding method. Summary of the Invention

[0006] The purpose of this application is to provide a method that effectively solves the above problems by changing the inherent feeding sequence.

[0007] In one aspect of this application, a method for preparing polyaryletherketones is provided, the method comprising:

[0008] a) A portion of the solid aromatic sulfone solvent is laid into the reactor, covering the bottom and part of the inner wall of the reactor;

[0009] b) Add reactants and optionally a catalyst, wherein the reactants include dihalobenzophenone and diphenol monomers, and the catalyst is an alkali metal carbonate;

[0010] c) Spread the remaining solid aromatic sulfone solvent onto the reactants obtained in step b), so that the reactants are completely covered by the aromatic sulfone solvent;

[0011] d) Under an inert atmosphere, the dihalobenzophenone is subjected to nucleophilic polycondensation with the diphenol monomer to obtain the polyarylether ketone;

[0012] The weight ratio of the solid aromatic sulfone solvent used in step a) to the remaining solid aromatic sulfone solvent in step c) is in the range of 2:1 to 3.5:1.

[0013] The molar ratio of the dihalobenzophenone to the diphenol monomer is in the range of 1.001-1.04:1, preferably in the range of 1.005-1.02:1.

[0014] In some embodiments according to this application, the alkali metal carbonate includes sodium carbonate or a mixture of sodium carbonate and potassium carbonate.

[0015] In some embodiments according to this application, the volume of the solid aromatic sulfone solvent used in step a) is 1 / 2 to 5 / 6 of the total volume of the reactor contents, preferably 2 / 3 to 5 / 6 of the total volume of the reactor contents.

[0016] In some embodiments of this application, the dihalobenzophenone is one or more of 4,4'-difluorobenzophenone, 2,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, and 2,4'-dichlorobenzophenone, preferably 4,4'-difluorobenzophenone.

[0017] In some embodiments of this application, the diphenol monomer includes one or more of hydroquinone, resorcinol, 2-methyl-1,4-hydroquinone, 2,2'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,4-naphthol, 1,5-naphthol, 2,6-naphthol, 2,7-naphthol, and 4,4'-dihydroxybenzophenone, preferably including one or more of hydroquinone, 4,4'-dihydroxybiphenyl, and 4,4'-dihydroxybenzophenone.

[0018] In some embodiments according to this application, the polyaryletherketone has a repeating unit shown in any one of the following formulas (I-1) to (I-3):

[0019]

[0020] In some embodiments according to this application, the alkali metal carbonate is a mixture of sodium carbonate and potassium carbonate, with a molar ratio of 40-55:1, preferably in the range of 45-50:1.

[0021] In some embodiments according to this application, when the polyaryletherketone has repeating units as shown in formula (I-3), an alkali metal carbonate as a catalyst is added in step d), and the alkali metal carbonate is sodium carbonate.

[0022] In some embodiments of this application, the aromatic sulfone solvent is selected from one or more of diphenyl sulfone, dibenzothiophene dioxide, phenoxthiophene dioxide, and 4-phenylsulfonyl biphenyl, preferably diphenyl sulfone.

[0023] In some embodiments according to this application, step d) is performed at a temperature of at least 190°C, involving nucleophilic polycondensation.

[0024] In some embodiments according to this application, the molar ratio of the alkali metal carbonate to the diphenol monomer is in the range of 1.001-1.25:1, preferably in the range of 1.05-1.2:1.

[0025] Another aspect of this application provides a polyaryletherketone obtained by the method described in the first aspect of this application, wherein the polyaryletherketone includes one or more of polyetheretherketone, biphenyl polyetheretherketone, polyetheretherketone-biphenyl polyetheretherketone copolymer, and polyetherketone.

[0026] In some embodiments according to this application, the polyaryletherketone satisfies at least one of the following:

[0027] (1) The melting point is 300-420℃, preferably 300-390℃, and more preferably 300-380℃;

[0028] (2) The glass transition temperature is 140-160℃, preferably 145-155℃;

[0029] (3) The density is 1-1.5 g / cm³, preferably 1.2-1.4 g / cm³.

[0030] A third aspect of this application provides a sheet material formed by extrusion of polyaryletherketone prepared according to the method of the first aspect of this application or polyaryletherketone prepared according to the second aspect of this application.

[0031] The fourth aspect of this application provides a tubing formed by extrusion of polyaryletherketone prepared according to the method of the first aspect of this application or polyaryletherketone prepared according to the second aspect of this application.

[0032] The fifth aspect of this application provides a prepreg prepared from polyaryletherketone according to the method of the first aspect of this application or from polyaryletherketone according to the second aspect of this application.

[0033] The plates, pipes, and prepregs of this application contain the polyaryletherketones provided in this application, and therefore have at least the same advantages as the polyaryletherketones. Detailed Implementation

[0034] The following detailed description discloses the method for preparing polyaryletherketones according to this application, the resulting polyaryletherketones, and embodiments of their related applications. However, unnecessary details may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of practically identical structures may be omitted. This is to avoid unnecessarily lengthy descriptions and to facilitate understanding by those skilled in the art. Furthermore, the following description is provided to enable those skilled in the art to fully understand this application and is not intended to limit the subject matter of the claims.

[0035] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0036] Unless otherwise specified, all embodiments and optional embodiments of this application may be combined with each other to form new technical solutions, and such technical solutions should be considered to be included in the disclosure of this application.

[0037] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions, and such technical solutions shall be deemed to be included in the disclosure of this application.

[0038] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the method may also include step (c), indicating that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0039] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0040] Unless otherwise specified, the term "or" is inclusive in this application. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0041] Unless otherwise specified, in this application, the terms "first," "second," "third," etc., are used to distinguish different objects, rather than to describe a specific order or primary / secondary relationship.

[0042] In this application, the terms "multiple", "various", etc., refer to two or more kinds.

[0043] Unless otherwise stated, the terms used in this application have the common meanings as commonly understood by those skilled in the art.

[0044] Unless otherwise stated, the values ​​of the parameters mentioned in this application can be determined using various testing methods commonly used in the art, for example, according to the testing methods given in the embodiments of this application. Unless otherwise stated, the test temperature is 25°C.

[0045] The term "halogenated" includes fluorine atoms, chlorine atoms, bromine atoms, etc.

[0046] Polyaryletherketones (PAEKs) have been widely used in defense, military, aerospace, electronics, petrochemical, medical, and automotive industries since their introduction due to their excellent comprehensive properties, including high heat resistance, radiation resistance, corrosion resistance, good dimensional stability, and superior electrical properties. The known synthesis techniques for PAEKs are mostly solution polymerization methods, primarily using diphenyl sulfone as a solvent and providing a suitable reaction medium environment for the stepwise polymerization of monomers under the catalysis of alkaline carbonates. The reaction mechanism of this synthesis process can be divided into two main stages: first, the bisphenol monomer reacts with carbonates under certain temperature conditions to generate the corresponding phenolate intermediate; subsequently, the phenolate undergoes a nucleophilic substitution reaction with dihalobenzophenone at a higher temperature, achieving stepwise chain extension and polymerization, ultimately forming high-molecular-weight PAEKs. This process requires stringent conditions and high precision control, but its clear reaction pathway and controllable product structure have made it one of the mainstream technologies for PAEK production.

[0047] For example, polyetheretherketone (PEEK) is typically polymerized at high temperatures using dihalobenzophenone and bisphenol monomers as comonomers in the presence of alkali metal salts and diphenyl sulfone as a solvent. The open reactor is usually heated by an electric heating mantle, so preheating is not performed. Instead, all reactants are added to the reactor at room temperature, and after half an hour of nitrogen protection, heating begins. Due to the limitations of the feeding method, the components in the reaction system remain solid when added to the reactor until heating to above 100°C melts the diphenyl sulfone and dihalobenzophenone, while the remaining reactants dissolve in the diphenyl sulfone solvent, forming a homogeneous liquid mixture, which then reacts at even higher temperatures.

[0048] This conventional feeding method, when heating solid mixtures, easily leads to uneven temperature distribution within the reactor, resulting in localized overheating or low heat transfer efficiency. If diphenyl sulfone is added first, it often melts and accumulates at the bottom of the reactor, while the upper reactants solidify into hard lumps after melting with dihalobenzophenone, preventing contact with the solvent. If the reactants are added first, they tend to remain unmelted for extended periods, resulting in slow solid-state heat transfer and localized overheating, leading to charring of the reactants at the bottom. These problems severely impact the efficiency of the polymerization reaction and the quality of the resulting product.

[0049] To address the aforementioned problems, the inventors of this application conducted extensive experiments and in-depth research, and surprisingly discovered that by changing the inherent feeding sequence, these problems were effectively solved. In this application, a solvent-reactant-solvent staged feeding method is adopted. This method ensures that the solvent is preferentially heated and melts, allowing the reactants to be completely coated with diphenyl sulfone. This ensures that the reactants do not directly contact the reactor walls (including the inner wall, bottom, and top end cap) throughout the reaction process. Because diphenyl sulfone has excellent thermal conductivity, it creates a uniform heat transfer environment, avoiding excessively high local temperatures caused by direct contact between the reactants and the reactor walls. Simultaneously, it promotes rapid and uniform dissolution of the reactants, effectively solving the technical problems of uneven heating, slow dissolution, and localized overheating and coking of reactants in traditional processes.

[0050] Therefore, a first aspect of the present application provides a method for preparing polyaryletherketones, the method comprising:

[0051] a) A portion of the solid aromatic sulfone solvent is laid into the reactor, covering the bottom and part of the inner wall of the reactor;

[0052] b) Add reactants and optionally a catalyst, wherein the reactants include dihalobenzophenone and diphenol monomers, and the catalyst is an alkali metal carbonate;

[0053] c) Spread the remaining solid aromatic sulfone solvent onto the reactants obtained in step b), so that the reactants are completely covered by the aromatic sulfone solvent;

[0054] d) Under an inert atmosphere, the dihalobenzophenone is subjected to nucleophilic polycondensation with the diphenol monomer to obtain the polyarylether ketone;

[0055] The weight ratio of the solid aromatic sulfone solvent used in step a) to the remaining solid aromatic sulfone solvent in step c) is in the range of 2:1 to 3.5:1; and

[0056] The molar ratio of the dihalobenzophenone to the diphenol monomer is in the range of 1.001-1.04:1, preferably in the range of 1.005-1.02:1.

[0057] Aromatic sulfone solvents are the dispersion medium in the synthesis of PAEK. The amount of solvent used at different stages of the reaction directly affects the solubility, heat transfer efficiency and subsequent separation difficulty of the reaction system. The weight ratio of the initial addition in step a) to the remaining amount in step c) is controlled within the range of 2:1 to 3.5:1, which is based on the dynamic requirements of the reaction process.

[0058] The PAEK synthesis reaction requires a dynamic process of "monomer dissolution - heating and polycondensation - product precipitation": Step a) Initially, add a sufficient amount of solid aromatic sulfone solvent to cover the bottom of the reactor, and then push the solvent outwards by stirring to form a concave structure with a low center and high edges; then add reactants and optional catalysts into the concave structure in the middle, and finally cover the remaining solvent to completely cover the reactants.

[0059] The principle of this application is based on the designed "solvent-reactant-solvent" feeding sequence, which generates a unique heat gradient transfer and gradual dissolution mechanism during heating. In step a), a sufficient amount of solid aromatic sulfone solvent is laid to cover the bottom and part of the inner wall of the reactor, then the reactants are added, and finally the remaining aromatic sulfone solvent is laid to completely cover the reactants with solvent, ensuring that the reactants do not come into direct contact with the reactor walls (including the inner wall, bottom and top end caps) throughout the reaction process.

[0060] Specifically, the heat gradient transfer and gradual dissolution mechanism described above are as follows:

[0061] (1) Layered heating and sequential melting: After heating begins in an inert gas atmosphere, the solvent at the bottom of the reactor is heated and melted first due to direct contact with the heat source, forming the bottom liquid phase; subsequently, the heat is gradually conducted upward through the bottom liquid phase and air convection, causing the top solvent to melt, so the reactants are wrapped in the middle layer and do not directly contact the high-temperature reactor inner wall.

[0062] (2) Physical isolation and indirect heat transfer: This structure allows the solid reactants to slowly heat up mainly by exchanging heat with the molten liquid aromatic sulfone solvent. The heat source is a mild liquid medium rather than solid conduction, thus achieving physical heat buffering.

[0063] (3) Dissolution from top to bottom and bottom to top: The aromatic sulfone solvent at the bottom melts and then wets the reactants from bottom to top, while the aromatic sulfone solvent at the top acts as a solid covering layer before final melting. When it melts, it dissolves the reactants from top to bottom. This bidirectional, gradual dissolution process ensures that the reactants are fully and uniformly wetted and dispersed under mild conditions.

[0064] In this application, "the reactants are completely covered by the solvent" means that the reactants (including bisphenol monomers, dihaloaromatic ketone monomers, alkali metal salts, reaction intermediates, and polymer melts) are essentially not in direct contact with the reactor walls (including the inner walls, bottom and top end caps) under the isolation effect of the aromatic sulfone solvent. That is, the actual contact area with the reactor walls (including the inner walls, bottom and top end caps) accounts for ≤5% of the total surface area of ​​the reactor walls, preferably ≤3%, more preferably ≤1%, even more preferably ≤0.5%, and most preferably no contact at all.

[0065] In some embodiments according to this application, the molar ratio of the dihalobenzophenone to the bisphenol monomer is in the range of 1.001-1.04:1, preferably in the range of 1.005-1.02:1. The dihalobenzophenone and the bisphenol monomer are the core reactive monomers in PAEK synthesis. They form the polymer backbone through nucleophilic substitution condensation polymerization, and their molar ratio directly affects the polymer's molecular weight, end-group structure, and mechanical properties. Using a molar ratio range of 1.001-1.04:1, and preferably 1.005-1.02:1, is based on the need to control the degree of polymerization and ensure product performance.

[0066] If the excess amount of dihalobenzophenone is insufficient, it cannot compensate for the monomer loss during the reaction process, potentially leading to incomplete reaction of some diphenol monomers and a decrease in polymer molecular weight. Furthermore, the end groups will be predominantly phenolic oxygen groups, making the product prone to degradation during high-temperature processing, resulting in discoloration and decreased mechanical strength. Conversely, if the excess amount of dihalobenzophenone is too high, a large amount of unreacted dihalobenzophenone will remain in the product, increasing the difficulty of subsequent separation and purification (requiring removal through solvent extraction, distillation, etc.). It will also cause the polymer end groups to be predominantly halogenated, reducing the product's chemical resistance and biocompatibility. Additionally, excess monomer will waste raw materials and increase production costs.

[0067] In some embodiments according to this application, the volume of the solid aromatic sulfone solvent used in step a) is 1 / 2 to 5 / 6 of the total volume of the reactor contents, preferably 2 / 3 to 5 / 6 of the total volume of the reactor contents.

[0068] The volume of the solid aromatic sulfone solvent used in step a) is limited to 1 / 2 to 5 / 6 of the total volume of the reactor contents. This is determined based on the encapsulation requirements of the reaction system, the reaction characteristics of the materials, and the compatibility with subsequent processes. If the volume is less than 1 / 2 of the total volume of the reactor contents, on the one hand, it is difficult to form a complete covering layer, which can easily lead to local exposure of the reactants, affecting the heat conduction and uniformity of the subsequent reaction; on the other hand, a thinner solvent layer is prone to damage and collapse in subsequent processes (such as heating), and cannot continuously provide stable protection and support for the reactants.

[0069] If the solvent layer volume exceeds 5 / 6 of the total reactor volume, it will result in redundant solid solvent usage, increasing production costs and potentially reducing heat transfer efficiency due to excessive solvent thickness. This can lead to uneven temperature distribution during subsequent heating, affecting the consistency of the reaction rate and the stability of the product performance. Strictly controlling the solvent layer volume within 1 / 2 to 5 / 6 of the total reactor volume ensures that the aromatic sulfone solvent completely covers the surface of the reactants after melting, effectively isolating them from external interference and providing a uniform reaction environment. It also balances heat transfer efficiency and the operability of subsequent processes, ensuring a stable and controllable reaction process. Furthermore, it optimizes solvent usage, achieving a balance between cost and effectiveness.

[0070] In some embodiments of this application, the alkali metal carbonate comprises sodium carbonate or a mixture of sodium carbonate and potassium carbonate. Potassium carbonate has high deprotonation activity, which can increase the reaction rate by 30%-50% in the initial stage, but it is also highly alkaline and easily undergoes side reactions with aromatic sulfone solvents in the later stages of high-temperature reactions, leading to solvent degradation and the formation of sulfide impurities, causing the PAEK product to turn yellow. Simultaneously, potassium carbonate is highly hygroscopic and easily clumps during storage, affecting the accuracy of feed addition. Sodium carbonate has lower activity, and the monomer conversion rate increases slowly in the initial stage of the polymerization reaction. To achieve a reaction rate comparable to potassium carbonate, the reaction temperature needs to be increased by 10-15°C, which not only increases energy consumption but may also lead to the volatilization loss of some monomers, resulting in a wider molecular weight distribution of the product. Therefore, in some embodiments of this application, the alkali metal carbonate is a mixture of sodium carbonate and potassium carbonate.

[0071] In some embodiments according to this application, the dihalobenzophenone is one or more of 4,4'-difluorobenzophenone, 2,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, and 2,4'-dichlorobenzophenone, preferably 4,4'-difluorobenzophenone. The strong electron-withdrawing effect of the fluorine substituent significantly enhances the electrophilicity of the carbonyl group, promoting efficient nucleophilic substitution reactions with the phenolic hydroxyl group. Furthermore, the reaction byproducts (fluoride salts) are easily separated from the solvent. Therefore, 4,4'-difluorobenzophenone is preferred, as its symmetrical structure is more conducive to forming regular polymer segments, further ensuring the structural uniformity and performance stability of the composite material.

[0072] In some embodiments of this application, the diphenol monomer includes one or more of hydroquinone, resorcinol, 2-methyl-1,4-hydroquinone, 2,2'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,4-naphthol, 1,5-naphthol, 2,6-naphthol, 2,7-naphthol, and 4,4'-dihydroxybenzophenone, preferably including one or more of hydroquinone, 4,4'-dihydroxybiphenyl, and 4,4'-dihydroxybenzophenone.

[0073] In some embodiments according to this application, the polyaryletherketone has a repeating unit shown in any one of the following formulas (I-1) to (I-3):

[0074]

[0075] In some embodiments according to this application, the alkali metal carbonate is a mixture of sodium carbonate and potassium carbonate. Using a mixture of sodium carbonate and potassium carbonate allows for a rapid initial reaction and a stable system in the later stages, which can be achieved by adjusting the ratio. The molar ratio of the two is in the range of 40-55:1, preferably in the range of 45-50:1. Compared to a single carbonate, this mixed alkali metal carbonate system can optimize the catalytic activity and compatibility of the reaction system through synergistic effects, effectively reduce the activation energy of the reaction, promote the full progress of the nucleophilic condensation reaction, reduce side reactions, and improve the molecular weight and structural uniformity of the polymer.

[0076] In some embodiments according to this application, when the polyaryletherketone has the repeating unit shown in formula (I-3), that is, when the polyaryletherketone is a polyetherketone, the alkali metal carbonate as a catalyst is added in step d) instead of in step b), and the alkali metal carbonate is sodium carbonate.

[0077] In some embodiments according to this application, aromatic sulfones are used as solvents. These solvents have advantages such as high boiling points, strong chemical stability, and good compatibility with the reactants. The aromatic sulfone solvent is selected from one or more of diphenyl sulfone, dibenzothiophene dioxide, phenoxthiophene dioxide, and 4-phenylsulfonyl biphenyl, preferably diphenyl sulfone. Such solvents have good solubility, can fully dissolve the reactants and the resulting polymers, avoid monomer aggregation or polymer precipitation, and ensure that the reaction proceeds efficiently in a homogeneous system.

[0078] To ensure the reaction system has a suitable viscosity, uniform heat and mass transfer, and complete reaction, the amount of aromatic sulfone solvent must be strictly controlled. Preferably, the weight of the aromatic sulfone solvent is three times or more than the weight of the dihalobenzophenone to avoid excessively high system viscosity that could hinder the reaction; simultaneously, it should not exceed ten times to prevent the monomer concentration from being too low, which could affect the polymerization rate and polymer molecular weight. Controlling the solvent weight within the above range ensures that the viscosity of the reaction system is within an appropriate range while avoiding environmental pollution and increased costs caused by excessive solvent.

[0079] In some embodiments according to this application, step d) is performed at a temperature of at least 190°C, involving nucleophilic polycondensation.

[0080] In some embodiments of this application, during the nucleophilic polycondensation, after all the reaction components, solvents, and alkali metal carbonates are added according to the method described, the temperature is first raised to 190°C and held for 20-40 minutes, then raised to 200°C and held for 20-40 minutes. This stage mainly realizes the salt formation reaction between the alkali metal carbonate and the phenolic hydroxyl group, laying the foundation for the subsequent polycondensation reaction. The temperature is then raised to 280°C and held for 50-70 minutes. At this temperature, the nucleophilic substitution reaction officially starts and gradually deepens, and the monomers gradually polymerize to form low molecular weight polymer chains. The temperature is then raised to 300°C and held for 50-65 minutes to promote the further growth of the polymer chains to the target molecular weight, while simultaneously balancing the reaction system to ensure a uniform molecular weight distribution of the polymer.

[0081] In some embodiments according to this application, the molar ratio of the alkali metal carbonate to the bisphenol monomer is in the range of 1.001-1.25:1, preferably in the range of 1.05-1.2:1. Within this range, the amount of alkali metal carbonate is slightly higher than that of the bisphenol monomer, which ensures that the bisphenol monomer is rapidly and completely converted into an active intermediate in the early stages of the reaction, increasing the polymerization rate. Furthermore, the alkalinity of the reaction system is moderate, which does not significantly inhibit the chain growth process of the polymerization reaction. The moderate amount of alkali metal carbonate can reduce the generation of side reaction impurities, resulting in a higher molecular weight and narrower molecular weight distribution of the polymer. This leads to better tensile strength, impact strength, heat distortion temperature, and other performance indicators of the product, and a lighter product color, meeting the stringent requirements for material appearance and performance in high-end applications.

[0082] The second aspect of this application provides a polyaryletherketone obtained by the method described in the first aspect of this application, wherein the polyaryletherketone includes one or more of polyetheretherketone, biphenyl polyetheretherketone, polyetheretherketone-biphenyl polyetheretherketone copolymer, and polyetherketone.

[0083] In some embodiments according to this application, the polyaryletherketone satisfies at least one of the following:

[0084] (1) The melting point is 300-420℃, preferably 300-390℃, more preferably 300-380℃, and even more preferably 300-340℃;

[0085] (2) The glass transition temperature is 140-160℃, preferably 145-155℃;

[0086] (3) The density is 1-1.5 g / cm³, preferably 1.2-1.4 g / cm³.

[0087] Furthermore, the crude polyarylether ketone particles obtained by the method described in the first aspect of this application, after preliminary purification but without further processing, are typically white or milky white, with a uniform color and no discolored spots. This pure and uniform color directly reflects the high purity and good initial quality of the product, indicating that the side reactions during the reaction process were properly controlled, and that the preliminary purification step effectively removed most impurities, oligomers, and residual solvents. Most importantly, the uniform particle color without any discolored spots not only signifies good batch stability and a relatively concentrated molecular weight distribution, but also lays a good foundation for subsequent deep processing (such as extrusion, injection molding, etc.), avoiding product performance fluctuations or appearance defects that may be caused by impurities or uneven color.

[0088] The polyaryletherketone obtained by the method according to this application has good mechanical properties and can be processed into intermediate products such as films, rods, sheets, and pipes. In addition to injection molding and compression molding, it can also be processed by extrusion and is suitable for preparing prepregs.

[0089] A third aspect of this application provides a sheet material formed by extrusion of polyaryletherketone prepared according to the method of the first aspect of this application or by extrusion of polyaryletherketone according to the second aspect of this application. In the context of this application, the term "sheet material" refers to an article of a flat, rectangular shape formed by extrusion, particularly melt extrusion.

[0090] A fourth aspect of this application provides a tubular material formed by extrusion of polyaryletherketone prepared according to the method of the first aspect of this application or by extrusion of polyaryletherketone according to the second aspect of this application. In the context of this application, the term "tubular material" refers to an article of an elongated tubular structure formed by extrusion, particularly melt extrusion.

[0091] A fifth aspect of this application provides a prepreg prepared from polyaryletherketone according to the method of the first aspect of this application or from polyaryletherketone according to the second aspect of this application. In the context of this application, the term "prepreg" refers to a composition of a resin matrix and a reinforcement formed by impregnating a resin matrix with fibers or fabrics that serve as continuous reinforcement, which is an intermediate material for manufacturing composite materials.

[0092] Compared with existing methods, the method of this application has the following significant advantages:

[0093] (1) Effectively prevent local overheating and coking: Since the reactants are isolated by solid aromatic sulfone solvent and do not directly contact the high temperature reactor wall, carbonization and coking caused by local overheating are fundamentally avoided, and the conversion rate of reactants and the purity of products are improved.

[0094] (2) Significantly improves dissolution efficiency and uniformity: The reactants are slowly and fully wetted by the liquid solvent in a loose state, which is conducive to their better dispersion and dissolution. After stirring is started, a uniform reaction system can be formed quickly, laying the foundation for obtaining polymer products with a narrower molecular weight distribution.

[0095] (3) Simple process and easy to operate: This method is achieved by optimizing the feeding sequence, without the need to add special equipment or complex control. It is easy to operate, has high stability, and is highly operable.

[0096] Example

[0097] The following embodiments describe the disclosure of this application in more detail. These embodiments are merely illustrative, as various modifications and variations will be apparent to those skilled in the art within the scope of the disclosure of this application. Unless otherwise stated, all parts, percentages, and ratios reported in the following embodiments are based on mass, and all reagents used in the embodiments are commercially available or synthesized by conventional methods and can be used directly without further processing, and the instruments used in the embodiments are commercially available.

[0098] The instruments used in the embodiments of this application include: a 3L electric heating jacket, a round-bottom open reactor, a stirring paddle, an electric stirrer, and a stirrer support. The electric heating jacket is a wrap-around heating system, with the heat source completely covering the body of the open reactor. The bottle opening (where it connects to the flange) and the portion above it are not subject to heat; therefore, they can be covered with absorbent cotton during heating to achieve heat preservation and accelerate temperature rise.

[0099] Unless otherwise stated, “room temperature” or “room temperature” as used herein refers to a temperature range of 15°C to 35°C, preferably 18°C ​​to 28°C; atmospheric pressure is standard atmospheric pressure; weighing is performed using an electronic balance; at room temperature, diphenyl sulfone is in the form of crystals, each crystal having a different volume, and is loosely packed with a large number of voids inside.

[0100] Test method:

[0101] 1) Melting point and glass transition temperature: The melting point and glass transition temperature of the polyaryletherketone prepared according to the embodiments and comparative examples of the present invention were determined by DSC testing.

[0102] Example 1: Preparation of PEEK-PEDEK

[0103] Experimental steps:

[0104] At room temperature, 1000 g of diphenyl sulfone solvent was weighed and added to a 3L round-bottom open reactor. A mechanical stirrer was inserted to push the diphenyl sulfone in the central area outwards, forming a central groove. Hydroquinone (167.51 g, 1.52 mol), 4,4'-dihydroxybiphenyl (94.43 g, 0.50 mol), 4,4'-difluorobenzophenone (449.68 g, 2.06 mol), sodium carbonate (245 g, 2.3 mol), and potassium carbonate (6.5 g, 0.05 mol) were added sequentially to the groove. Then, 425 g of diphenyl sulfone was weighed and spread on top of all the solid reactants, essentially filling the reactor.

[0105] Install the reactor lid, tighten the flange seal, connect the mechanical stirrer and nitrogen gas conduit, and insert the thermometer probe into the material. Check the stopper to ensure a good seal. Purge nitrogen into the reaction system at a flow rate of 140-160 mL / min for 30 minutes to completely displace the air. After displacement, place the reactor in a 3L electric heating mantle and begin heating, covering the bottle opening with absorbent cotton for additional insulation.

[0106] Observe and record the heating process:

[0107] Heating for approximately 10 minutes: The volume of solid material inside the reactor decreased significantly, and the top layer of diphenyl sulfone began to slide downwards. At this point, the thermometer reading did not show a significant increase, and the solid material remained loose. Gently lifting the reactor revealed the formation of a pale yellow, transparent liquid at the bottom.

[0108] Heating for approximately 20 minutes: A large amount of liquid phase appears in the system. Removing some of the absorbent cotton allows direct observation of the liquid from above. Simultaneously, solid clumps of reactants can be seen forming around the stir bar; these clumps can be easily broken up with a wire. At this point, the thermometer reading rises to approximately 120°C.

[0109] Heat for about 30 minutes: large pieces of solid have mostly disappeared, leaving only scattered small pieces. At this point, start stirring; the thermometer reading should be around 140°C.

[0110] Subsequently, the stirring speed was increased to 0.10 kr / h, and the temperature was continuously raised to 180℃ and maintained for one hour. The temperature was then raised to 190℃ and held for 30 minutes; subsequently, it was raised to 200℃ and held for another 30 minutes. The mixture inside the reactor was a light yellow, opaque, homogeneous mixture with low viscosity. The temperature was further increased to 280℃ for polymerization, and maintained for one hour. The solution viscosity increased significantly, so the stirring rate was increased, and the temperature was raised to 300℃ and maintained for one hour. The solution was then poured into a wide iron pan for cooling and crystallization.

[0111] Experimental results and characterization:

[0112] After the reaction was complete, the product was poured out of the reactor. The initial product was a light gray viscous liquid, which solidified into a white solid upon cooling. After pulverization, washing with acetone and deionized water, white PEEK-PEDEK particles were obtained. Visual inspection showed that the final product had a uniform color and consistent texture, with no visible black charring spots.

[0113] The obtained product was subjected to DSC and density tests. The product had a melting point of 301℃, a glass transition temperature of 150.9℃, and a density of 1.30 g / cm³. After injection molding, the product yielded a uniformly colored part with no obvious discoloration.

[0114] Comparative Example 1

[0115] Experimental steps:

[0116] At room temperature, hydroquinone (167.51 g, 1.52 mol), 4,4'-dihydroxybiphenyl (94.43 g, 0.50 mol), 4,4'-difluorobenzophenone (449.68 g, 2.06 mol), sodium carbonate (245 g, 2.3 mol), and potassium carbonate (6.5 g, 0.05 mol) were added directly to a 3L open glass reactor, along with 1425 g of diphenyl sulfone solvent, until the reactor was almost completely filled.

[0117] Install the four-port reactor cap, tighten the flange seal, connect the mechanical stirrer and nitrogen gas delivery line, and insert the thermometer probe into the material. Check the stopper to ensure a good seal. Purge nitrogen into the reaction system at a flow rate of 140-160 mL / min for 30 minutes to completely displace the air. After displacement, place the reaction apparatus in a 3L electric heating mantle and begin heating, covering the flask opening with absorbent cotton for additional insulation.

[0118] Observe and record the heating process:

[0119] After heating for about 10 minutes, the amount of solid material in the reactor decreased significantly, and the top layer of diphenyl sulfone began to slide down. At this time, the thermometer reading did not rise significantly, and the solid material remained loose. When the reactor was lifted, a small amount of liquid could be seen on the bottle wall.

[0120] After heating for about 20 minutes, a burnt smell was emitted, the solids did not decrease significantly, and the thermometer reading rose to about 50°C. Attempts to remove the thermometer were unsuccessful.

[0121] After heating for about 30 minutes, a distinct burnt smell was emitted, but the thermometer reading did not rise significantly. Lifting the reactor revealed obvious charring at the bottom, with severely clumped contents and only a small amount of liquid remaining. Returning the reactor to the heating jacket and lifting the agitator caused the upper layer of diphenyl sulfone to slide off. Using a wire to forcefully break up the clumped material, the diphenyl sulfone began to melt, and the temperature rose.

[0122] Heating for about 50 minutes will cause diphenyl sulfone to basically melt, and the solution will be dark brown. Increase the stirring speed to 0.10 kr / h and continue to raise the temperature to 180℃, maintaining the constant temperature for one hour.

[0123] One hour later, the temperature was raised to 190°C and kept constant for half an hour. Then the temperature was raised to 200°C and kept constant for half an hour, resulting in a light yellow, opaque solution with low viscosity.

[0124] The temperature was raised again to 280℃, and the polymerization reaction was maintained at this temperature for 1 hour. The viscosity of the solution did not change significantly. The temperature was then raised to 300℃, and the reaction was continued for one hour to terminate the reaction.

[0125] Experimental results and characterization:

[0126] After the reaction was complete, the product was poured out of the reactor. The product was a brown liquid with low viscosity and was prone to splashing upon pouring. After cooling, it was crushed and washed with acetone and water. It was found that most of the product pulverized during the washing process and was difficult to form into particles. The product morphology was clearly substandard and was not tested.

[0127] Example 2: Preparation of PEEK

[0128] Experimental steps:

[0129] At room temperature, 1000 g of diphenyl sulfone solvent was weighed and added to a 3L round-bottom open reactor. A mechanical stirrer was inserted to push the diphenyl sulfone in the central area outwards, forming a central groove. Hydroquinone (223.40 g, 2 mol), 4,4'-difluorobenzophenone (447.5 g, 2.02 mol), sodium carbonate (245 g, 2.3 mol), and potassium carbonate (6.5 g, 0.05 mol) were added to the groove in sequence. Then, 425 g of diphenyl sulfone was weighed and spread on top of all the solid reactants, essentially filling the reactor.

[0130] Install the four-port reactor cover, tighten the flange seals, connect the mechanical stirrer and nitrogen gas conduit, insert the electric dipole temperature probe, and check the airtightness of the apparatus. Introduce nitrogen gas into the reaction system at a flow rate of 140-160 mL / min for 30 minutes, continuing the nitrogen inlet flow. Place the reactor in a 3L electric heating mantle to begin heating.

[0131] Observe and record the heating process:

[0132] After heating for about 10 minutes, the amount of solid material in the reactor decreased significantly, and the top layer of diphenyl sulfone began to slide down. The thermometer reading rose slightly. The thermometer could be easily removed. Lifting the reactor revealed a pale yellow, transparent liquid at the bottom.

[0133] After heating for approximately 20 minutes, a large amount of liquid phase appeared in the system. Removing some of the absorbent cotton allowed direct observation of the liquid from above. Simultaneously, solid clumps of reactants were observed forming around the stir bar; these clumps could be easily broken up with a wire. The thermometer reading rose to 120°C.

[0134] After heating for approximately 30 minutes, the large solid pieces largely disappeared, leaving only scattered small pieces. At this point, stirring was started, and the thermometer reading was approximately 140°C. The temperature was increased to 190°C and maintained for 30 minutes; then increased to 200°C and maintained for another 30 minutes. The mixture in the reactor was a light yellow, opaque, homogeneous mixture with low viscosity. The temperature was further increased to 280°C for polymerization, and maintained for one hour. The solution viscosity increased significantly; the stirring rate was increased, and the temperature was increased to 300°C, maintained for one hour. The solution was then poured into a wide iron pan for cooling and crystallization.

[0135] Experimental results and characterization:

[0136] After the reaction was complete, the product was poured out of the reactor. The initial product was a light gray viscous liquid, which solidified into a white solid upon cooling. This solid was then pulverized, washed with acetone, and finally washed with deionized water to obtain white polyetheretherketone (PEEK) particles. The final product had a uniform color and consistent texture, with no visible black charring spots.

[0137] The obtained product was subjected to relevant tests. The product had a melting point of 321.2℃, a glass transition temperature of 148.5℃, and a density of 1.30 g / cm³.

[0138] Comparative Example 2

[0139] Experimental steps:

[0140] At room temperature, hydroquinone (223.40 g, 2 mol), 4,4'-difluorobenzophenone (447.5 g, 2.02 mol), sodium carbonate (245 g, 2.3 mol), and potassium carbonate (6.5 g, 0.05 mol) were added directly to a 3L open glass reactor, along with 1425 g of diphenyl sulfone solvent, until the reactor was almost completely filled.

[0141] Install the four-port reactor lid, tighten the flange seal, connect the mechanical stirrer and nitrogen gas delivery line, and insert the thermometer probe into the material. Check the stopper to ensure a good seal. Purge nitrogen into the reaction system at a flow rate of 140-160 mL / min for 30 minutes to completely displace the air. After displacement, place the reaction apparatus in a 3L electric heating mantle and begin heating, covering the flask opening with absorbent cotton for additional insulation.

[0142] Observe and record the heating process:

[0143] After heating for about 10 minutes, the amount of solid material in the reactor decreased significantly, and the top layer of diphenyl sulfone began to slide down. At this time, the thermometer reading did not rise significantly, and the solid material remained in a loose state. When the reactor was lifted, a small amount of liquid could be seen on the bottle wall.

[0144] After heating for about 20 minutes, a burnt smell was emitted, the solids did not decrease significantly, and the thermometer reading rose to about 50°C. Attempts to remove the thermometer were unsuccessful.

[0145] After heating for about 30 minutes, a distinct burnt smell was emitted, but the thermometer reading did not rise significantly. Upon lifting the reactor, obvious charring was observed at the bottom, with severe clumping of the chemicals and only a small amount of liquid remaining. The reactor was placed back into the heating jacket, and the agitator was lifted; the upper layer of diphenyl sulfone slid off. Using a wire to forcefully break up the clumped material, the diphenyl sulfone began to melt, and the temperature rose.

[0146] Heating for about 50 minutes will cause diphenyl sulfone to basically melt, and the solution will be dark brown. Increase the stirring speed to 0.10 kr / h and continue to raise the temperature to 180℃, maintaining the constant temperature for one hour.

[0147] One hour later, the temperature was raised to 190°C and kept constant for half an hour. Then the temperature was raised to 200°C and kept constant for half an hour, resulting in a light yellow, opaque solution with low viscosity.

[0148] The temperature was raised again to 280℃, and the polymerization reaction was maintained at this temperature for 1 hour. The viscosity of the solution did not change significantly. The temperature was then raised to 300℃, and the reaction was continued for one hour to terminate the reaction.

[0149] Experimental results and characterization:

[0150] After the reaction was complete, the product was poured out of the reactor. The product was a brown liquid with low viscosity and was prone to splashing when poured out. After cooling, it was crushed and washed with acetone and water. It was found that most of the product pulverized during the washing process and was difficult to form into particles.

[0151] Example 3: Preparation of PEK

[0152] Experimental steps:

[0153] At room temperature, 1000 g of diphenyl sulfone solvent was weighed and added to a 3L round-bottom open reactor. A mechanical stirrer was inserted to push the diphenyl sulfone in the central area outwards, forming a central groove. 4,4'-dihydroxybenzophenone (337.15 g) and 4,4'-difluorobenzophenone (346.84 g) were then added sequentially to the groove. Subsequently, 298.5 g of diphenyl sulfone was weighed and spread on top of all the solid reactants, essentially filling the reactor.

[0154] Install the four-port reactor cap, tighten the flange seal, connect the mechanical stirrer and nitrogen gas delivery line, and insert the thermometer probe into the material. Check the stopper to ensure a good seal. Purge nitrogen into the reaction system at a flow rate of 140-160 mL / min for 30 minutes to completely displace the air. After displacement, place the reaction apparatus in a 3L electric heating mantle and begin heating, covering the flask opening with absorbent cotton for additional insulation.

[0155] Observe and record the heating process:

[0156] Heating for approximately 10 minutes: The volume of solid material inside the reactor decreased significantly, and the top layer of diphenyl sulfone began to slide downwards. At this point, the thermometer reading did not show a significant increase, and the solid material remained loose. Gently lifting the reactor revealed the formation of a pale yellow, transparent liquid at the bottom.

[0157] Heating for approximately 20 minutes: A large amount of liquid phase appears in the system. Removing some of the absorbent cotton allows direct observation of the liquid from above. Simultaneously, solid clumps of reactants can be seen forming around the stir bar; these clumps can be easily broken up with a wire. At this point, the thermometer reading rises to approximately 120°C.

[0158] Heat for about 30 minutes: large pieces of solid have mostly disappeared, leaving only scattered small pieces. At this point, start stirring; the thermometer reading should be around 140°C.

[0159] Subsequently, the stirring speed was increased to 0.10 kr / h, and the temperature was continuously raised to 180℃.

[0160] 185.11g of sodium carbonate was added gradually. Upon addition, the solution rapidly changed from clear to a pale yellow turbid liquid. With the addition of sodium carbonate, a large number of bubbles were generated, and the temperature slightly decreased. The temperature was kept constant, and after 1 hour, it was raised to 250℃ and reacted at this temperature for 0.5 hours, at which point the solution turned deep yellow. The temperature was then raised again to 320℃ and kept constant for 1 hour, at which point the reaction was terminated.

[0161] Experimental results and characterization:

[0162] After the reaction was complete, the product was poured out of the reactor. The initial product was a light yellow viscous liquid, which solidified into a light yellow solid upon cooling. After pulverization, washing with acetone and deionized water, milky white polyetherketone (PEK) particles were obtained. The final product had a uniform color and consistent texture, with no visible black charring spots.

[0163] The obtained product was subjected to DSC testing, and the melting point of the product was found to be 380℃, with no obvious glass transition.

[0164] The polyaryletherketone prepared according to the method of this application has a uniform color and consistent texture, and is free of visible black charring spots, making it suitable for applications such as extruding sheets and rods and preparing prepregs.

[0165] Some exemplary implementations are described below:

[0166] Implementation Method 1. A method for preparing polyaryletherketones, the method comprising:

[0167] a) A portion of the solid aromatic sulfone solvent is laid into the reactor, covering the bottom and part of the inner wall of the reactor;

[0168] b) Add reactants and optionally a catalyst, wherein the reactants include dihalobenzophenone and diphenol monomers, and the catalyst is an alkali metal carbonate;

[0169] c) Spread the remaining solid aromatic sulfone solvent onto the reactants obtained in step b), so that the reactants are completely covered by the aromatic sulfone solvent;

[0170] d) Under an inert atmosphere, the dihalobenzophenone is subjected to nucleophilic polycondensation with the diphenol monomer to obtain the polyarylether ketone;

[0171] The weight ratio of the solid aromatic sulfone solvent used in step a) to the remaining solid aromatic sulfone solvent in step c) is in the range of 2:1 to 3.5:1.

[0172] The molar ratio of the dihalobenzophenone to the diphenol monomer is in the range of 1.001-1.04:1, preferably in the range of 1.005-1.02:1.

[0173] Implementation Method 2. The method as described in Implementation Method 1, wherein the alkali metal carbonate comprises sodium carbonate or a mixture of sodium carbonate and potassium carbonate.

[0174] Implementation Method 3. The method as described in Implementation Method 1 or 2, wherein the volume of the solid aromatic sulfone solvent used in step a) is 1 / 2 to 5 / 6 of the total volume of the reactor contents, preferably 2 / 3 to 5 / 6 of the total volume of the reactor contents.

[0175] Embodiment 4. The method as described in any one of Embodiments 1 to 3, wherein the dihalobenzophenone is one or more of 4,4'-difluorobenzophenone, 2,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone and 2,4'-dichlorobenzophenone, preferably 4,4'-difluorobenzophenone.

[0176] Embodiment 5. The method as described in any one of Embodiments 1 to 4, wherein the diphenol monomer comprises one or more of hydroquinone, resorcinol, 2-methyl-1,4-hydroquinone, 2,2'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,4-naphthol, 1,5-naphthol, 2,6-naphthol, 2,7-naphthol, and 4,4'-dihydroxybenzophenone, preferably comprising one or more of hydroquinone, 4,4'-dihydroxybiphenyl, and 4,4'-dihydroxybenzophenone.

[0177] Embodiment 6. The method as described in any one of Embodiments 1 to 5, wherein the polyaryletherketone has a repeating unit shown in any one of the following formulas (I-1) to (I-3):

[0178]

[0179] Implementation Method 7. The method as described in any one of Implementation Methods 1 to 5, wherein the alkali metal carbonate is a mixture of sodium carbonate and potassium carbonate, and the molar ratio of the two is in the range of 40-55:1, preferably in the range of 45-50:1.

[0180] Embodiment 8. The method as described in Embodiment 6, wherein when the polyaryletherketone has repeating units as shown in Formula (I-3), an alkali metal carbonate as a catalyst is added in step d), and the alkali metal carbonate is sodium carbonate.

[0181] Embodiment 9. The method as described in any one of Embodiments 1 to 8, wherein the aromatic sulfone solvent is selected from one or more of diphenyl sulfone, dibenzothiophene dioxide, phenoxthiophene dioxide and 4-phenylsulfonyl biphenyl, preferably diphenyl sulfone.

[0182] Implementation 10. The method as described in any one of Implementations 1 to 9, wherein step d) is performed at a temperature of at least 190°C.

[0183] Implementation Method 11. The method as described in any one of Implementation Methods 1 to 10, wherein the molar ratio of the alkali metal carbonate to the diphenol monomer is in the range of 1.001-1.25:1, preferably in the range of 1.05-1.2:1.

[0184] Embodiment 12. A polyaryletherketone obtained by the method of any one of Embodiments 1 to 11, wherein the polyaryletherketone includes one or more of polyetheretherketone, biphenyl polyetheretherketone, polyetheretherketone-biphenyl polyetheretherketone copolymer, and polyetherketone.

[0185] Embodiment 13. The polyaryletherketone as described in Embodiment 12, wherein the polyaryletherketone satisfies at least one of the following:

[0186] (1) The melting point is 300-420℃, preferably 300-390℃, and more preferably 300-380℃;

[0187] (2) The glass transition temperature is 140-160℃, preferably 145-155℃;

[0188] (3) The density is 1-1.5 g / cm³, preferably 1.2-1.4 g / cm³.

[0189] Embodiment 14. A sheet material formed by extrusion of polyaryletherketone prepared by the method of any one of Embodiments 1 to 11 or polyaryletherketone described in Embodiment 12 or 13.

[0190] Embodiment 15. A tubing formed by extrusion of polyaryletherketone prepared by the method of any one of Embodiments 1 to 11 or polyaryletherketone described in Embodiment 12 or 13.

[0191] Embodiment 16. A prepreg prepared from polyaryletherketone prepared by the method of any one of Embodiments 1 to 11 or from polyaryletherketone as described in Embodiment 12 or 13.

[0192] Although this application has been described with reference to numerous embodiments and examples, those skilled in the art will recognize from the disclosure of this application that other embodiments can be designed without departing from the protection scope of this application.

Claims

1. A method for preparing polyaryletherketones, the method comprising: a) A portion of the solid aromatic sulfone solvent is laid into the reactor, covering the bottom and part of the inner wall of the reactor; b) Add reactants and catalyst, wherein the reactants include dihalobenzophenone and diphenol monomers, and the catalyst is an alkali metal carbonate; c) Spread the remaining solid aromatic sulfone solvent onto the reactants obtained in step b), so that the reactants are completely covered by the aromatic sulfone solvent; d) Under an inert atmosphere, the dihalobenzophenone is subjected to nucleophilic polycondensation with the diphenol monomer to obtain the polyarylether ketone; The weight ratio of the solid aromatic sulfone solvent used in step a) to the remaining solid aromatic sulfone solvent in step c) is in the range of 2:1 to 3.5:

1. The molar ratio of the dihalobenzophenone to the diphenol monomer is in the range of 1.001-1.04:1; In step a), the volume of the solid aromatic sulfone solvent used is 1 / 2 to 5 / 6 of the total volume of the reactor contents. The aromatic sulfone solvent is diphenyl sulfone; The molar ratio of the alkali metal carbonate to the diphenol monomer is in the range of 1.001-1.25:

1.

2. The method as described in claim 1, wherein, The molar ratio of the dihalobenzophenone to the diphenol monomer is in the range of 1.005-1.02:

1.

3. The method as described in claim 1 or 2, wherein, The alkali metal carbonates include sodium carbonate or a mixture of sodium carbonate and potassium carbonate.

4. The method as described in claim 1 or 2, wherein, The volume of the solid aromatic sulfone solvent used in step a) is 2 / 3 to 5 / 6 of the total volume of the reactor contents.

5. The method as described in claim 1 or 2, wherein, The dihalobenzophenone is one or more of 4,4'-difluorobenzophenone, 2,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, and 2,4'-dichlorobenzophenone.

6. The method as described in claim 1 or 2, wherein, The dihalobenzophenone is 4,4'-difluorobenzophenone.

7. The method as described in claim 1 or 2, wherein, The diphenol monomers include one or more of hydroquinone, resorcinol, 2-methyl-1,4-hydroquinone, 2,2'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,4-naphthol, 1,5-naphthol, 2,6-naphthol, 2,7-naphthol, and 4,4'-dihydroxybenzophenone.

8. The method as claimed in claim 1 or 2, wherein, The diphenol monomers include one or more of hydroquinone, 4,4'-dihydroxybiphenyl, and 4,4'-dihydroxybenzophenone.

9. The method as claimed in claim 1 or 2, wherein, The polyaryletherketone has a repeating unit shown in any one of the following formulas (I-1) to (I-3):

10. The method as claimed in claim 1 or 2, wherein, The alkali metal carbonate is a mixture of sodium carbonate and potassium carbonate, with a molar ratio between the two in the range of 40-55:

1.

11. The method as claimed in claim 1 or 2, wherein, The alkali metal carbonate is a mixture of sodium carbonate and potassium carbonate, with a molar ratio of 45-50:

1.

12. The method of claim 9, wherein, When the polyaryletherketone has the repeating unit shown in formula (I-3), an alkali metal carbonate as a catalyst is added in step d), and the alkali metal carbonate is sodium carbonate.

13. The method as claimed in claim 1 or 2, wherein, Step d) involves nucleophilic polycondensation at a temperature of at least 190°C.

14. The method as claimed in claim 1 or 2, wherein, The molar ratio of the alkali metal carbonate to the diphenol monomer is in the range of 1.05-1.2:

1.

15. The polyarylether ketone obtained by the method of any one of claims 1 to 14, wherein, The polyaryletherketone includes one or more of polyetheretherketone, biphenyl polyetheretherketone, polyetheretherketone-biphenyl polyetheretherketone copolymer, and polyetherketone.

16. The polyaryletherketone of claim 15, wherein, The polyaryletherketone satisfies at least one of the following: (1) The melting point is 300-420℃ according to DSC test; (2) The glass transition temperature is 140-160℃ according to DSC test; (3) The density is 1-1.5 g / cm³.

17. The polyaryletherketone of claim 15, wherein, The polyaryletherketone satisfies at least one of the following: (1) The melting point is 300-390℃ according to DSC test; (2) The glass transition temperature is 145-155℃ according to DSC test; (3) The density is 1.2-1.4 g / cm³.

18. The polyaryletherketone according to any one of claims 15 to 17, wherein the melting point is 300-380°C as determined by DSC.

19. A sheet material formed by extrusion of polyaryletherketone prepared by the method of any one of claims 1 to 14 or polyaryletherketone as described in any one of claims 15 to 18.

20. A tubing formed by extrusion of polyaryletherketone prepared by the method of any one of claims 1 to 14 or polyaryletherketone as described in any one of claims 15 to 18.

21. A prepreg prepared from polyaryletherketone prepared by the method of any one of claims 1 to 14 or from polyaryletherketone prepared by any one of claims 15 to 18.

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