Bio-based polyether-ether-ketone as well as preparation method and application thereof

Abstract

The invention relates to the technical field of high polymer materials, and particularly discloses bio-based polyether-ether-ketone as well as a preparation method and application thereof. The preparation method of the bio-based polyether-ether-ketone provided by the invention comprises the following steps: mixing a bio-based diphenol monomer, alkali, 4, 4 '-difluorobenzophenone, a water-carrying agent and a polar organic solvent, refluxing at 30-150 DEG C to carry out water carrying, steaming out the water-carrying agent at 40-150 DEG C, carrying out final polymerization reaction at 150-260 DEG C, and sequentially precipitating, washing and drying to obtain the bio-based polyether-ether-ketone. The bio-based polyether-ether-ketone is obtained. According to the bio-based polyether-ether-ketone provided by the invention, a core molecular structure is constructed by taking renewable biomass as a raw material, the core performance of high temperature resistance and chemical corrosion resistance of traditional polyether-ether-ketone is reserved, and the dissolving property and the processing fluidity are optimized and improved.

Description

A bio-based polyether ether ketone, its preparation method and application Technical Field

[0001] This application relates to the field of polymer materials technology, specifically disclosing a bio-based polyether ether ketone, its preparation method, and its applications. Background Technology

[0002] Polyetheretherketone (PEEK), as a high-performance specialty engineering plastic, occupies an important position in key fields such as aerospace, petrochemicals, automotive manufacturing, and engineering machinery due to its excellent properties such as high temperature resistance, wear resistance, and chemical corrosion resistance. Currently, the synthesis of PEEK mainly relies on the nucleophilic substitution reaction between bisphenol and 4,4'-difluorobenzophenone. However, most of the bisphenol monomers used are derived from petroleum-based raw materials, posing significant problems such as non-renewable resources, substantial environmental impact during production, and potential toxicity and health risks.

[0003] Although the industry has attempted to adjust the melting point, crystallinity, toughness, and thermal properties of polymers by introducing diphenols with different structures, such as bisphenol A, 4,4'-biphenylhydrazine, dihydroxydiphenyl sulfone, and their derivatives, the synthesis routes of these monomers are still based on petrochemicals and have failed to fundamentally address the sustainability challenges. Driven by the global trend of carbon neutrality and sustainable development, the development of bio-based polyetheretherketones (PEEKs) using renewable biomass resources has become a research hotspot in the industry. However, existing bio-based alternatives generally face technical bottlenecks, making it difficult to simultaneously achieve high bio-based content, excellent thermal properties, and good processability, thus failing to meet the stringent requirements of high-end fields for comprehensive material performance. Summary of the Invention

[0004] In view of this, this application provides a bio-based polyether ether ketone, its preparation method and application. This application uses bio-based diphenol monomers made from renewable biomass resources to achieve synergistic optimization of high bio-based content, excellent thermal properties and good processability of the material.

[0005] The first aspect of this application provides a method for preparing bio-based polyether ether ketone, comprising the following steps: mixing a bio-based bisphenol monomer, an alkali, 4,4'-difluorobenzophenone, a dehydrating agent, and a polar organic solvent, refluxing the mixture at 30-150°C to remove water, then distilling off the dehydrating agent at 40-150°C, and then carrying out a final polymerization reaction at 150-260°C, followed by precipitation, washing, and drying to obtain bio-based polyether ether ketone.

[0006] Preferably, the preparation method of the bio-based diphenol monomer includes the following steps: mixing the bio-based phenol monomer, aldehyde-ketone condensation monomer, acidic catalyst and anhydrous ethanol, and carrying out a condensation reaction at 30-80°C, followed by filtration, washing and drying to obtain the bio-based diphenol monomer.

[0007] Preferably, the bio-based phenolic monomer is selected from one or more of carvacrol, eugenol, guaiacol, lignin, resveratrol, or thymol.

[0008] Preferably, the aldehyde-ketone condensation monomer is selected from one or more of p-methylbenzaldehyde, furfural, benzaldehyde, p-chlorobenzaldehyde, p-bromobenzaldehyde, p-nitrobenzaldehyde, p-aminobenzaldehyde, anisaldehyde, 1-naphthaldehyde, 9-fluorenone, 9-anthrone, veratral, or benzophenone.

[0009] Preferably, the acidic catalyst is selected from one or more of sulfuric acid, hydrochloric acid, phosphoric acid, aluminum trichloride, or zinc dichloride.

[0010] Preferably, the mass-to-volume ratio of the bio-based phenol monomer, aldehyde-ketone condensation monomer, acidic catalyst and anhydrous ethanol is 1 g : (0.3-0.7) g : (0.1-0.4) mL : (2-4) mL.

[0011] Preferably, the condensation reaction takes 8-30 hours.

[0012] Preferably, the alkali is selected from one or more of sodium hydroxide, potassium hydroxide, pyridine, triethylamine, piperidine, sodium carbonate, potassium carbonate, or cesium carbonate.

[0013] Preferably, the water-removing agent is selected from one or more of toluene, xylene, or anisole.

[0014] Preferably, the polar organic solvent is selected from one or more of sulfolane, N-methylpyrrolidone, or diphenyl sulfone.

[0015] Preferably, the molar mass-volume ratio of the bio-based diphenol monomer, alkali, 4,4'-difluorobenzophenone, dehydrating agent and polar organic solvent is 1 mmol: (1-3) mmol: (0.9-1.1) mmol: (24-30.625) g: (5-6.25) mL.

[0016] Preferably, the reflux water carrying time is 1-6 hours.

[0017] Preferably, the distillation time for the water-containing agent is 0.5-2 hours.

[0018] Preferably, the final polymerization reaction takes 8-25 hours.

[0019] The second aspect of this application provides a bio-based polyether ether ketone, prepared by the aforementioned method for preparing bio-based polyether ether ketone.

[0020] The bio-based polyetheretherketone (PEEK) provided in this application uses renewable biomass as a raw material to construct its core molecular structure. It retains the core properties of traditional PEEK, such as high-temperature resistance and chemical corrosion resistance, while optimizing and improving its solubility and processing flowability. The bio-based PEEK provided in this application can eliminate dependence on petroleum-derived raw materials, reduce fossil resource consumption and environmental impact, and simultaneously meet the molding and processing requirements of precision components. Therefore, compared with existing technologies, the bio-based PEEK provided in this application is resource-sustainable, has stable thermal properties, good processing adaptability, balanced overall performance, and a wide range of applications. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1 is the infrared spectrum of the bio-based polyether ether ketone provided in Example 1 of this application; Figure 2 is the nuclear magnetic resonance spectrum of the bio-based polyether ether ketone provided in Example 1 of this application; Figure 3 is the glass transition temperature spectrum of the bio-based polyether ether ketone provided in Example 1 of this application; Figure 4 is the thermal decomposition temperature spectrum of the bio-based polyether ether ketone provided in Example 1 of this application; Figure 5 is the gel permeation chromatogram of the bio-based polyether ether ketone provided in Example 1 of this application; Figure 6 is the infrared spectrum of the bio-based bisphenol A provided in Example 1 of this application; Figure 7 is the nuclear magnetic resonance spectrum of the bio-based bisphenol A provided in Example 1 of this application. Detailed Implementation

[0023] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. Furthermore, it should be understood that the specific embodiments described herein are only for illustration and explanation of this application and are not intended to limit this application.

[0024] In this application, unless otherwise stated, directional terms such as "upper" and "lower" generally refer to the upper and lower positions of the device in its actual use or operating state, specifically the orientation shown in the accompanying drawings; while "inner" and "outer" refer to the outline of the device. Furthermore, in the description of this application, the term "comprising" means "including but not limited to". The terms first, second, third, etc., are used merely as illustrative purposes and do not impose numerical requirements or establish a numerical order.

[0025] In this application, "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural.

[0026] In this application, "at least one" means one or more, and "more than one" means two or more. "One or more", "at least one of the following", or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0027] Various embodiments of this application may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is referred to herein, it means including any referenced number (fraction or integer) within the referred range.

[0028] The present application will be specifically described below through specific embodiments. The following embodiments are only some embodiments of the present application and are not intended to limit the present application.

[0029] In a first aspect, this application provides a method for preparing bio-based polyether ether ketone, the technical solution of which is as follows: A method for preparing bio-based polyether ether ketone includes the following steps: mixing bio-based bisphenol monomer, alkali, 4,4'-difluorobenzophenone, dehydrating agent and polar organic solvent, refluxing at 30-150°C to remove water, then evaporating the dehydrating agent at 40-150°C, and then carrying out a final polymerization reaction at 150-260°C, followed by precipitation, washing and drying to obtain bio-based polyether ether ketone.

[0030] It should be noted that this preparation method uses renewable bio-based bisphenol monomers as the core raw material to achieve the synthesis of bio-based polyether ether ketones. The entire process requires no special or complex equipment, is simple and easy to control, and can meet the needs of large-scale production. The bio-based bisphenol monomer serves as the core building block of the polymerization reaction. Its phenolic hydroxyl groups, under the activation of a base, form nucleophilic centers that undergo a nucleophilic substitution reaction with 4,4'-difluorobenzophenone. A dehydrating agent removes the water content from the reaction mixture, and a polar organic solvent maintains a homogeneous reaction system.

[0031] To ensure uniform reaction, the mixing of raw materials is crucial. In practice, a suitable reaction vessel can be selected based on the production scale. The bio-based bisphenol monomer, alkali, 4,4'-difluorobenzophenone, dehydrating agent, and polar organic solvent are added sequentially in a molar mass-to-volume ratio of 1 mmol:(1-3) mmol:(0.9-1.1) mmol:(24-30.625) g:(5-6.25) mL. The components are thoroughly mixed using mechanical stirring or ultrasonic dispersion to avoid abnormal polymerization caused by uneven local concentrations. For example, in laboratory-scale preparation, a round-bottom four-necked flask can be used as the reaction vessel, equipped with a magnetic stirrer to achieve uniform mixing. In industrial-scale production, a reaction vessel with a mechanical stirrer can be selected to ensure mixing efficiency and system uniformity.

[0032] In some embodiments, the alkali may be one or more of sodium hydroxide, potassium hydroxide, pyridine, triethylamine, piperidine, sodium carbonate, potassium carbonate, or cesium carbonate.

[0033] In some embodiments, the polar organic solvent may be one or more of sulfolane, N-methylpyrrolidone, or diphenyl sulfone.

[0034] The reflux dehydration reaction is used to remove the water generated during the reaction process, shifting the reaction equilibrium to the right. The temperature in this step is controlled between 30-150℃. This temperature range ensures efficient water removal by forming an azeotrope with the dehydrating agent while preventing premature side reactions in the raw materials due to excessively high temperatures. Under the heating conditions of the reflux reaction in this application, the dehydrating agent and water form an azeotrope and evaporate together. After condensation, the azeotrope enters a water separator. Because the density of the dehydrating agent is less than that of water, the water is discharged from the lower layer of the separator, while the dehydrating agent flows back into the reflux reaction apparatus, continuously carrying away water from the reflux reaction system and achieving efficient dehydration.

[0035] In some embodiments, the dehydrating agent may be one or more of toluene, xylene, or anisole. These dehydrating agents have suitable azeotropic temperatures with water and good compatibility with the reaction system, and will not adversely affect subsequent polymerization reactions. The reflux dehydration time is typically 1-6 hours, and the specific duration can be flexibly adjusted according to the amount of water generated in the reaction system to ensure sufficient water removal. For example, it can be any two values ​​between 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, or more.

[0036] The removal of the dehydrating agent needs to be carried out at 40-150℃ and maintained for 0.5-2 hours to completely remove the dehydrating agent from the system. The temperature of this step should be slightly higher than the boiling point of the dehydrating agent, but lower than the starting temperature of the subsequent final polymerization reaction to avoid residual dehydrating agent affecting the structure and properties of the polymer. For example, when toluene is used as the dehydrating agent, its boiling point is approximately 110.6℃, and the temperature of this step can be controlled at 115-120℃ to ensure rapid and complete removal of the dehydrating agent, while avoiding unnecessary side reactions caused by excessively high system temperatures. Under the heating conditions for removing the dehydrating agent in this application, the dehydrating agent is rapidly removed, shortening the removal time and facilitating the recycling and reuse of the dehydrating agent.

[0037] In the final polymerization reaction, bio-based polyether ether ketone (PEEK) polymer chains are formed at a temperature controlled between 150-260℃ for 8-25 hours. This temperature range activates the nucleophilic substitution reaction, allowing the bio-based bisphenol monomer to fully react with 4,4'-difluorobenzophenone to form bio-based PEEK. During the reaction, the presence of a base continuously activates the phenolic hydroxyl groups of the bio-based bisphenol monomer, promoting the continuous progress of the reaction; polar organic solvents provide a stable homogeneous environment, which is beneficial to the growth and extension of the polymer chains. For example, polar organic solvents such as sulfolane, N-methylpyrrolidone, or diphenyl sulfone exhibit good solubility and thermal stability, remaining stable under the high-temperature conditions of the final polymerization reaction.

[0038] In some embodiments, the final polymerization reaction is carried out under stirring conditions, with a stirring speed of 50-200 r / min.

[0039] Post-treatment steps including precipitation, washing, and drying are used to purify the product and remove unreacted monomers, catalysts, and other impurities. In the precipitation step, the reaction product is poured into a solution such as hot water or anhydrous ethanol to rapidly precipitate the polymer. In the washing step, the precipitate is boiled and washed 2-3 times with deionized water to ensure complete removal of impurities. The drying step is typically carried out in a vacuum drying oven at 60-100℃ for 5-12 hours to thoroughly remove residual solvents and moisture from the product, yielding a high-purity, stable bio-based polyether ether ketone.

[0040] In some embodiments, the preparation method of the bio-based diphenol monomer includes the following steps: mixing the bio-based phenol monomer, aldehyde-ketone condensation monomer, acidic catalyst and anhydrous ethanol, and carrying out a condensation reaction at 30-80°C, followed by filtration, washing and drying to obtain the bio-based diphenol monomer.

[0041] Among them, bio-based phenolic monomers refer to phenolic hydroxyl compounds derived from renewable biomass resources, which serve as the core raw materials for synthesizing bio-based diphenol monomers; aldehyde-ketone condensation monomers refer to compounds containing aldehyde or ketone groups, which are used to undergo condensation reactions with bio-based phenolic monomers to construct diphenol structures; acidic catalysts refer to acidic substances that can promote condensation reactions, while anhydrous ethanol serves as a reaction medium to provide a homogeneous reaction environment.

[0042] Specifically, this application synthesizes bio-based diphenol monomers through a condensation reaction of bio-based phenol monomers and aldehyde-ketone condensation monomers under the action of an acidic catalyst. The acidic catalyst activates the carbonyl group of the aldehyde-ketone condensation monomer through protonation, enhancing its electrophilic activity and thus promoting the nucleophilic addition-elimination reaction with the ortho- and para-position hydrogens of the phenolic hydroxyl group of the bio-based phenol monomer, forming a diphenol structure linked by a methylene or benzylidene group. Anhydrous ethanol is used as a solvent, which not only dissolves the reactants to ensure system homogeneity but also regulates the reaction rate by adjusting the polarity of the reaction environment, avoiding the formation of byproducts due to excessively vigorous local reactions. The reaction temperature range of 30-80℃ balances reaction efficiency and selectivity; lower temperatures reduce side reactions, while higher temperatures accelerate the reaction process, and this range can be adjusted according to the specific monomer combination. After the reaction is completed, unreacted reactants, catalysts, and trace impurities are removed through a post-processing procedure of filtration, washing, and drying to obtain high-purity bio-based diphenol monomers.

[0043] In some embodiments, the bio-based phenolic monomer is selected from one or more of carvacrol, eugenol, guaiacol, lignin, resveratrol, or thymol. These bio-based phenolic monomers are widely found in renewable resources such as plant essential oils and lignin degradation products, making them abundant and environmentally friendly. The phenolic hydroxyl groups in their molecular structures have good reactivity, while the substituents on the benzene ring can regulate the structure and properties of the polymer through steric hindrance and electronic effects.

[0044] In some embodiments, the aldehyde-ketone condensation monomers are selected from one or more of p-methylbenzaldehyde, furfural, benzaldehyde, p-chlorobenzaldehyde, p-bromobenzaldehyde, p-nitrobenzaldehyde, p-aminobenzaldehyde, anisaldehyde, 1-naphthaldehyde, 9-fluorenone, 9-anthrone, veratral, or benzophenone. The structural characteristics of these monomers directly affect the linkage mode and spatial configuration of bio-based bisphenol monomers. For example, furfural, as a typical bio-based aldehyde monomer, can introduce its furan ring structure into the polymer backbone to increase the bio-based content; the strong electron-withdrawing group of p-nitrobenzaldehyde can enhance the condensation reaction activity; and the rigid aromatic ring structure of 9-fluorenone can improve the thermal stability and mechanical strength of the polymer. The acidic catalyst is selected from one or more of sulfuric acid, hydrochloric acid, phosphoric acid, aluminum trichloride, or zinc dichloride. Among these, protic acids such as sulfuric acid and hydrochloric acid have high catalytic efficiency and low cost, while Lewis acids such as aluminum trichloride and zinc dichloride have higher selectivity for condensation reactions. The catalyst can be flexibly selected according to the solubility of the reaction system and the reaction requirements.

[0045] In some embodiments, the mass-to-volume ratio of the bio-based phenol monomer, aldehyde-ketone condensation monomer, acidic catalyst, and anhydrous ethanol is 1 g : (0.3-0.7) g : (0.1-0.4) mL : (2-4) mL.

[0046] Post-treatment steps including filtration, washing, and drying are used to purify the product and remove unreacted monomers, catalysts, and other impurities. The washing step involves washing the filter cake 2-3 times with a 1:1 volume ratio of ethanol and water to ensure complete removal of impurities. The drying step is typically carried out in a vacuum drying oven at 60-100°C for 3-8 hours to thoroughly remove residual solvents and moisture from the product, yielding high-purity, stable bio-based polyether ether ketone.

[0047] In some embodiments, the condensation reaction is carried out under stirring conditions, with a stirring speed of 50-300 r / min.

[0048] Secondly, this application provides the aforementioned bio-based polyether ether ketone.

[0049] This bio-based polyetheretherketone (PEEK) uses bio-based bisphenol monomers derived from renewable biomass resources as its core unit, forming a stable polymer chain structure through polymerization. It retains the high-temperature resistance, chemical corrosion resistance, and good mechanical strength of traditional petroleum-based PEEK, while improving the material's solubility and processing fluidity through structural optimization of the bio-based monomers. This solves the problem of existing bio-based alternatives struggling to balance high bio-based content with excellent overall performance. Simultaneously, this material eliminates dependence on petroleum-derived feedstocks, reducing fossil resource consumption and environmental impact during production.

[0050] Thirdly, this application provides the application of the above-mentioned bio-based polyether ether ketone in the preparation of high-temperature resistant, wear-resistant, and corrosion-resistant components.

[0051] Specifically, this application applies bio-based polyether ether ketone to the preparation of high-temperature resistant, wear-resistant, and corrosion-resistant components, enabling them to maintain structural stability and functional integrity under high-temperature conditions in aerospace, petrochemical, and other fields. For example, it can be used to prepare high-temperature resistant engine seals, chemical reactor liners, and other components, which can withstand long-term high-temperature environments without deformation or performance degradation.

[0052] In addition, the excellent processing fluidity of this bio-based polyether ether ketone allows it to be used to manufacture precision parts with different structures through various molding processes such as injection molding, extrusion, and compression molding, meeting the needs of aerospace, automotive manufacturing, engineering machinery, and electronics industries for component molding precision and complex structures.

[0053] The present application will be specifically described below through specific embodiments. These embodiments are only some embodiments of the present application and are not intended to limit the present application. Embodiment 1

[0054] This embodiment provides a method for preparing bio-based polyether ether ketone, specifically including the following steps: Under a nitrogen atmosphere, bio-based bisphenol A (3.1083 g, 0.8 mmol), 4,4'-difluorobenzophenone (1.7456 g, 0.8 mmol), cesium carbonate (4.5616 g, 1.4 mmol), 19.5 g sulfolane, and 5 mL toluene are added sequentially to a 100 mL dry round-bottom four-necked flask equipped with a mechanical stirrer and a water-separating condenser. The temperature is raised to 120 °C, refluxed to remove water for 2 h, and then raised to 140 °C. The reaction is continued for 0.5 h, toluene is distilled off, and the temperature is raised to 190 °C. The reaction is continued at 50 r / min for 14 h until completion, yielding a viscous polymer solution. The polymer solution was poured into hot water while still hot to precipitate, washed three times with deionized water by boiling, and dried in a vacuum oven at 80℃ for 8 hours to obtain bio-based polyether ether ketone. The infrared spectrum of this bio-based polyether ether ketone is shown in Figure 1, the nuclear magnetic resonance spectrum is shown in Figure 2, the glass transition temperature spectrum is shown in Figure 3, the thermal decomposition temperature spectrum is shown in Figure 4, the gel permeation chromatogram is shown in Figure 5, and the solubility is shown in Table 1.

[0055] Table 1 Item NMPTHFDMAcDMFDMSODCHCHCl3EAACN Example 1 Bio-based polyether ether ketone solubility Excellent Very Good Very Good Insoluble Excellent Excellent Very Good Insoluble The preparation method of the bio-based diphenol monomer described in the table includes the following steps: Under a nitrogen atmosphere, carvacrol (25 g, 0.166 mol), benzaldehyde (8.83 g, 0.083 mol), 5 mL concentrated sulfuric acid, and 50 mL anhydrous ethanol were added sequentially to a 100 mL dry round-bottom four-necked flask equipped with a mechanical stirrer and a water-separating condenser. The mixture was heated to 75 °C and stirred at 50 r / min for 8 h. After the reaction was completed, the mixture was cooled to room temperature, filtered to obtain a filter cake, washed three times with ethanol and deionized water in a 1:1 volume ratio, and dried in a vacuum oven at 80 °C for 5 h to obtain the bio-based diphenol monomer (26.89 g, yield 83.45%). The infrared spectrum of this bio-based diphenol monomer is shown in Figure 6, and the nuclear magnetic resonance spectrum is shown in Figure 7. Example 2

[0056] This embodiment provides a method for preparing bio-based polyether ether ketone, specifically including the following steps: Under a nitrogen atmosphere, bio-based bisphenol A (3.1083 g, 0.8 mmol), 4,4'-difluorobenzophenone (1.7456 g, 0.8 mmol), potassium carbonate (2.0732 g, 1.5 mmol), 19.5 g sulfolane, and 5 mL toluene are added sequentially to a 100 mL dry round-bottom four-necked flask equipped with a mechanical stirrer and a water-separating condenser. The temperature is raised to 120 °C, refluxed to remove water for 2 h, and then raised to 140 °C for 1 h. The toluene is distilled off, and the temperature is raised to 190 °C. The reaction is carried out at 50 r / min for 14 h until completion, yielding a viscous polymer solution. The polymer solution is poured into hot water while hot to precipitate, washed three times with deionized water by boiling, and dried in a vacuum oven at 80 °C for 8 h to obtain bio-based polyether ether ketone.

[0057] The preparation method of the bio-based diphenol monomer includes the following steps: Under a nitrogen atmosphere, thymol (25g, 0.166mol), benzaldehyde (8.83g, 0.083mol), 5mL concentrated sulfuric acid, and 50mL anhydrous ethanol are added sequentially to a 100mL dry round-bottom four-necked flask equipped with a mechanical stirrer and a water-separating condenser. The mixture is heated to 75℃ and stirred at 100r / min for 8h. After the reaction is completed, it is cooled to room temperature, filtered to obtain a filter cake, and washed three times with ethanol and deionized water in a 1:1 volume ratio. The filter cake is then dried in a vacuum oven at 80℃ for 5h to obtain the bio-based diphenol monomer (29.73g, yield 92.26%). Example 3

[0058] This embodiment provides a method for preparing bio-based polyether ether ketone, specifically including the following steps: Under a nitrogen atmosphere, bio-based bisphenol A (3.3839 g, 0.8 mmol), 4,4'-difluorobenzophenone (1.7456 g, 0.8 mmol), potassium carbonate (2.0732 g, 1.5 mmol), 20.5 g sulfolane, and 5 mL toluene are added sequentially to a 100 mL dry round-bottom four-necked flask equipped with a mechanical stirrer and a water-separating condenser. The temperature is raised to 120 °C, refluxed to remove water for 2 h, and then raised to 140 °C for 1.5 h. The toluene is distilled off, and the temperature is raised to 190 °C. The reaction is carried out at 100 r / min for 14 h until completion, yielding a viscous polymer solution. The polymer solution is poured into hot water while hot to precipitate, washed three times with deionized water by boiling, and dried in a vacuum oven at 80 °C for 8 h to obtain bio-based polyether ether ketone.

[0059] The preparation method of the bio-based diphenol monomer includes the following steps: Under a nitrogen atmosphere, thymol (25g, 0.166mol), 9-fluorenone (14.96g, 0.083mol), 5mL concentrated sulfuric acid, and 50mL anhydrous ethanol are added sequentially to a 100mL dry round-bottom four-necked flask equipped with a mechanical stirrer and a water-separating condenser. The mixture is heated to 75℃ and stirred at 150r / min for 10h. After the reaction is completed, the mixture is cooled to room temperature, filtered to obtain a filter cake, washed three times with ethanol and deionized water in a 1:1 volume ratio, and dried in a vacuum oven at 80℃ for 5h to obtain the bio-based diphenol monomer (26.73g, yield 76.21%). Example 4

[0060] This embodiment provides a method for preparing bio-based polyether ether ketone, specifically including the following steps: Under a nitrogen atmosphere, bio-based bisphenol A (3.5887 g, 0.8 mmol), 4,4'-difluorobenzophenone (1.7456 g, 0.8 mmol), potassium carbonate (2.0732 g, 1.5 mmol), 22.5 g sulfolane, and 5 mL toluene are added sequentially to a 100 mL dry round-bottom four-necked flask equipped with a mechanical stirrer and a water-separating condenser. The temperature is raised to 120 °C, refluxed to remove water for 2 h, and then raised to 140 °C and reacted for 2 h. The toluene is distilled off, and the temperature is further raised to 195 °C and reacted at 150 r / min for 18 h until completion, yielding a viscous polymer solution. The polymer solution is poured into hot water while hot to precipitate, washed three times with deionized water by boiling, and dried in a vacuum oven at 80 °C for 8 h to obtain bio-based polyether ether ketone.

[0061] The preparation method of the bio-based diphenol monomer includes the following steps: Under a nitrogen atmosphere, thymol (25g, 0.166mol), veratral (13.79g, 0.083mol), 5mL concentrated sulfuric acid, and 50mL anhydrous ethanol are added sequentially to a 100mL dry round-bottom four-necked flask equipped with a mechanical stirrer and a water-separating condenser. The mixture is heated to 75℃ and stirred at 200r / min for 9h. After the reaction is completed, it is cooled to room temperature, filtered to obtain a filter cake, and washed three times with ethanol and deionized water in a volume ratio of 1:1. The filter cake is then dried in a vacuum oven at 80℃ for 5h to obtain the bio-based diphenol monomer (29.22g, yield 78.49%). Example 5

[0062] This embodiment provides a method for preparing bio-based polyether ether ketone, specifically including the following steps: Under a nitrogen atmosphere, bio-based bisphenol A (2.6883 g, 0.8 mmol), 4,4'-difluorobenzophenone (1.7456 g, 0.8 mmol), potassium carbonate (2.0732 g, 1.5 mmol), 19.2 g sulfolane, and 5 mL toluene are added sequentially to a 100 mL dry round-bottom four-necked flask equipped with a mechanical stirrer and a water-separating condenser. The temperature is raised to 120 °C, refluxed to remove water for 2 h, and then raised to 140 °C for 1 h. The toluene is distilled off, and the temperature is raised to 190 °C. The reaction is carried out at 200 r / min for 15 h until completion, yielding a viscous polymer solution. The polymer solution is poured into hot water while hot to precipitate, washed three times with deionized water by boiling, and dried in a vacuum oven at 80 °C for 8 h to obtain bio-based polyether ether ketone.

[0063] The preparation method of the bio-based diphenol monomer includes the following steps: Under a nitrogen atmosphere, guaiacol (25 g, 0.201 mol), benzaldehyde (10.7 g, 0.101 mol), 10 mL concentrated hydrochloric acid, and 50 mL anhydrous ethanol are added sequentially to a 100 mL dry round-bottom four-necked flask equipped with a mechanical stirrer and a water-separating condenser. The mixture is heated to 75 °C and stirred at 250 r / min for 8 h. After the reaction is completed, the mixture is cooled to room temperature, filtered to obtain a filter cake, washed three times with ethanol and deionized water in a 1:1 volume ratio, and dried in a vacuum oven at 80 °C for 5 h to obtain the bio-based diphenol monomer (31.76 g, yield 93.5%). Example 6

[0064] This embodiment provides a method for preparing bio-based polyether ether ketone, specifically including the following steps: Under a nitrogen atmosphere, bio-based bisphenol A (2.8034 g, 0.8 mmol), 4,4'-difluorobenzophenone (1.7456 g, 0.8 mmol), potassium carbonate (2.0732 g, 1.5 mmol), 20.7 g sulfolane, and 5 mL toluene are added sequentially to a 100 mL dry round-bottom four-necked flask equipped with a mechanical stirrer and a water-separating condenser. The temperature is raised to 120 °C, refluxed to remove water for 2 h, and then raised to 140 °C and reacted for 1 h. The toluene is distilled off, and the temperature is raised to 195 °C and reacted at 100 r / min for 14 h until completion, yielding a viscous polymer solution. The polymer solution is poured into hot water while hot to precipitate, washed three times with deionized water by boiling, and dried in a vacuum oven at 80 °C for 8 h to obtain bio-based polyether ether ketone.

[0065] The preparation method of the bio-based diphenol monomer includes the following steps: Under a nitrogen atmosphere, guaiacol (25 g, 0.201 mol), p-methylbenzaldehyde (12.13 g, 0.101 mol), 10 mL concentrated hydrochloric acid, and 50 mL anhydrous ethanol are added sequentially to a 100 mL dry round-bottom four-necked flask equipped with a mechanical stirrer and a water-separating condenser. The mixture is heated to 75 °C and stirred at 300 r / min for 10 h. After the reaction is completed, the mixture is cooled to room temperature, filtered to obtain a filter cake, washed three times with ethanol and deionized water in a 1:1 volume ratio, and dried in a vacuum oven at 80 °C for 5 h to obtain the bio-based diphenol monomer (31.55 g, yield 89.17%). Example 7

[0066] This embodiment provides a method for preparing bio-based polyether ether ketone, specifically including the following steps: Under a nitrogen atmosphere, bio-based bisphenol A (3.0512 g, 0.8 mmol), 4,4'-difluorobenzophenone (1.7456 g, 0.8 mmol), potassium carbonate (2.0732 g, 1.5 mmol), 19.5 g sulfolane, and 5 mL toluene are added sequentially to a 100 mL dry round-bottom four-necked flask equipped with a mechanical stirrer and a water-separating condenser. The temperature is raised to 120 °C, refluxed to remove water for 2 h, and then raised to 140 °C and reacted for 1 h. Toluene is distilled off, and the temperature is raised to 195 °C and reacted at 100 r / min for 14 h until completion, yielding a viscous polymer solution. The polymer solution is poured into hot water while hot to precipitate, washed three times with deionized water by boiling, and dried in a vacuum oven at 80 °C for 8 h to obtain bio-based polyether ether ketone.

[0067] The preparation method of the bio-based diphenol monomer includes the following steps: Under a nitrogen atmosphere, guaiacol (25 g, 0.201 mol), p-nitrobenzaldehyde (15.26 g, 0.101 mol), 10 mL concentrated hydrochloric acid, and 50 mL anhydrous ethanol are added sequentially to a 100 mL dry round-bottom four-necked flask equipped with a mechanical stirrer and a water-separating condenser. The mixture is heated to 75 °C and stirred at 200 r / min for 9 h. After the reaction is completed, the mixture is cooled to room temperature, filtered to obtain a filter cake, washed three times with ethanol and deionized water in a 1:1 volume ratio, and dried in a vacuum oven at 80 °C for 5 h to obtain the bio-based diphenol monomer (25.13 g, yield 65.24%). Example 8

[0068] This embodiment provides a method for preparing bio-based polyether ether ketone, specifically including the following steps: Under a nitrogen atmosphere, bio-based bisphenol A (3.2822 g, 0.8 mmol), 4,4'-difluorobenzophenone (1.7456 g, 0.8 mmol), cesium carbonate (4.5616 g, 1.4 mmol), 24.5 g sulfolane, and 5 mL toluene are added sequentially to a 100 mL dry round-bottom four-necked flask equipped with a mechanical stirrer and a water-separating condenser. The temperature is raised to 120 °C, refluxed to remove water for 2 h, and then raised to 140 °C for 1 h. The toluene is distilled off, and the temperature is raised to 200 °C. The reaction is carried out at 100 r / min for 20 h until completion, yielding a viscous polymer solution. The polymer solution is poured into hot water while hot to precipitate, washed three times with deionized water by boiling, and dried in a vacuum oven at 80 °C for 8 h to obtain bio-based polyether ether ketone.

[0069] The preparation method of the bio-based diphenol monomer includes the following steps: Under a nitrogen atmosphere, guaiacol (25 g, 0.201 mol), p-aminobenzaldehyde (12.23 g, 0.101 mol), 10 mL concentrated hydrochloric acid, and 50 mL anhydrous ethanol are added sequentially to a 100 mL dry round-bottom four-necked flask equipped with a mechanical stirrer and a water-separating condenser. The mixture is heated to 75 °C and stirred at 200 r / min for 12 h. After the reaction is completed, the mixture is cooled to room temperature, filtered to obtain a filter cake, washed three times with ethanol and deionized water in a 1:1 volume ratio, and dried in a vacuum oven at 80 °C for 5 h to obtain the bio-based diphenol monomer (19.83 g, yield 55.89%). Example 9

[0070] This embodiment provides a method for preparing bio-based polyether ether ketone, specifically including the following steps: Under a nitrogen atmosphere, bio-based bisphenol A (2.9314 g, 0.8 mmol), 4,4'-difluorobenzophenone (1.7456 g, 0.8 mmol), potassium carbonate (2.0732 g, 1.5 mmol), 21.3 g sulfolane, and 5 mL toluene are added sequentially to a 100 mL dry round-bottom four-necked flask equipped with a mechanical stirrer and a water-separating condenser. The temperature is raised to 120 °C, refluxed to remove water for 2 h, and then raised to 140 °C and reacted for 1 h. The toluene is distilled off, and the temperature is further raised to 195 °C and reacted at 100 r / min for 15 h until completion, yielding a viscous polymer solution. The polymer solution is poured into hot water while hot to precipitate, washed three times with deionized water by boiling, and dried in a vacuum oven at 80 °C for 8 h to obtain bio-based polyether ether ketone.

[0071] The preparation method of the bio-based diphenol monomer includes the following steps: Under a nitrogen atmosphere, guaiacol (25 g, 0.201 mol), anisaldehyde (13.75 g, 0.101 mol), 10 mL concentrated hydrochloric acid, and 50 mL anhydrous ethanol are added sequentially to a 100 mL dry round-bottom four-necked flask equipped with a mechanical stirrer and a water-separating condenser. The mixture is heated to 75 °C and stirred at 200 r / min for 9 h. After the reaction is completed, the mixture is cooled to room temperature, filtered to obtain a filter cake, washed three times with ethanol and deionized water in a 1:1 volume ratio, and dried in a vacuum oven at 80 °C for 5 h to obtain the bio-based diphenol monomer (30.58 g, yield 82.64%). Example 10

[0072] This embodiment provides a method for preparing bio-based polyether ether ketone, specifically including the following steps: Under a nitrogen atmosphere, bio-based bisphenol A (3.9645 g, 1 mmol), 4,4'-difluorobenzophenone (2.182 g, 1 mmol), cesium carbonate (4.5616 g, 1.4 mmol), 28 g sulfolane, and 5 mL toluene are added sequentially to a 100 mL dry round-bottom four-necked flask equipped with a mechanical stirrer and a water-separating condenser. The temperature is raised to 120 °C, refluxed to remove water for 2 h, and then raised to 140 °C and reacted for 1 h. The toluene is distilled off, and the temperature is further raised to 195 °C and reacted at 100 r / min for 16 h until completion, yielding a viscous polymer solution. The polymer solution is poured into hot water while hot to precipitate, washed three times with deionized water by boiling, and dried in a vacuum oven at 80 °C for 8 h to obtain bio-based polyether ether ketone.

[0073] The preparation method of the bio-based diphenol monomer includes the following steps: Under a nitrogen atmosphere, guaiacol (25g, 0.201mol), veratral (16.78g, 0.101mol), 10mL concentrated hydrochloric acid, and 50mL anhydrous ethanol are added sequentially to a 100mL dry round-bottom four-necked flask equipped with a mechanical stirrer and a water-separating condenser. The mixture is heated to 75℃ and stirred at 200r / min for 9h. After the reaction is completed, the mixture is cooled to room temperature, filtered to obtain a filter cake, and washed three times with ethanol and deionized water in a volume ratio of 1:1. The filter cake is then dried in a vacuum oven at 80℃ for 5h to obtain the bio-based diphenol monomer (28.03g, yield 70.01%).

[0074] The technical solutions provided by the embodiments of this application have been described in detail above. Specific examples have been used to illustrate the principles and implementation methods of this application. The description of the above embodiments is only for the purpose of helping to understand the method and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. A method for preparing bio-based polyether ether ketone, characterized in that, The process includes the following steps: mixing a bio-based diphenol monomer, an alkali, 4,4'-difluorobenzophenone, a dehydrating agent, and a polar organic solvent, refluxing the mixture at 30-150°C to remove water, then distilling off the dehydrating agent at 40-150°C, followed by a final polymerization reaction at 150-260°C, and then sequentially performing precipitation, washing, and drying to obtain a bio-based polyether ether ketone. The bio-based phenol monomer used in the preparation of the bio-based diphenol monomer is selected from one or more of carvacrol, eugenol, guaiacol, lignin, resveratrol, or thymol.

2. The method for preparing bio-based polyether ether ketone according to claim 1, characterized in that, The preparation method of the bio-based diphenol monomer includes the following steps: mixing the bio-based phenol monomer, aldehyde-ketone condensation monomer, acidic catalyst and anhydrous ethanol, and carrying out a condensation reaction at 30-80℃, followed by filtration, washing and drying to obtain the bio-based diphenol monomer.

3. The method for preparing bio-based polyether ether ketone according to claim 2, characterized in that, The aldehyde-ketone condensation monomers are selected from one or more of p-methylbenzaldehyde, furfural, benzaldehyde, p-chlorobenzaldehyde, p-bromobenzaldehyde, p-nitrobenzaldehyde, p-aminobenzaldehyde, anisaldehyde, 1-naphthaldehyde, 9-fluorenone, 9-anthrone, veratral, or benzophenone; and / or the acid catalyst is selected from one or more of sulfuric acid, hydrochloric acid, phosphoric acid, aluminum trichloride, or zinc dichloride.

4. The method for preparing bio-based polyether ether ketone according to claim 2, characterized in that, The mass-to-volume ratio of the bio-based phenol monomer, aldehyde-ketone condensation monomer, acidic catalyst, and anhydrous ethanol is 1 g : (0.3-0.7) g : (0.1-0.4) mL : (2-4) mL.

5. The method for preparing bio-based polyether ether ketone according to claim 2, characterized in that, The condensation reaction takes 8-30 hours.

6. The method for preparing bio-based polyether ether ketone according to claim 1, characterized in that, The alkali is selected from one or more of sodium hydroxide, potassium hydroxide, pyridine, triethylamine, piperidine, sodium carbonate, potassium carbonate, or cesium carbonate; and / or the dehydrating agent is selected from one or more of toluene, xylene, or anisole; and / or the polar organic solvent is selected from one or more of sulfolane, N-methylpyrrolidone, or diphenyl sulfone.

7. The method for preparing bio-based polyether ether ketone according to claim 1, characterized in that, The molar mass-volume ratio of the bio-based diphenol monomer, alkali, 4,4'-difluorobenzophenone, dehydrating agent and polar organic solvent is 1 mmol: (1-3) mmol: (0.9-1.1) mmol: (24-30.625) g: (5-6.25) mL.

8. The method for preparing bio-based polyether ether ketone according to claim 1, characterized in that, The reflux water removal time is 1-6 hours; and / or the distillation water removal agent time is 0.5-2 hours; and / or the final polymerization reaction time is 8-25 hours.

9. A bio-based polyetheretherketone, characterized in that, It is prepared by the method of any one of claims 1-8 for preparing bio-based polyether ether ketone.

10. The application of the bio-based polyether ether ketone of claim 9 in the preparation of high-temperature resistant, wear-resistant, and corrosion-resistant components.

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