Bio-based polyaryletherketone and preparation method thereof

Abstract

The invention relates to the technical field of polyaryletherketone, in particular to bio-based polyaryletherketone and a preparation method thereof.The preparation method comprises the following steps that a 4, 4 '-difluorobenzophenone monomer and a diphenol monomer are dissolved in a reaction solvent in the presence of a salt-forming agent, the temperature is increased, an aromatic nucleophilic polycondensation reaction is conducted, and the bio-based polyaryletherketone is obtained; the diphenol monomer is a combination of soybean flavone and one or more of hydroquinone, resorcinol, 4, 4 '-biphenol, 4, 4'-dihydroxybenzophenone and bisphenol A; the diphenol monomer is a combination of soybean flavone and one or more of hydroquinone, resorcinol, 4, 4 '-biphenol, 4, 4'-dihydroxybenzophenone and bisphenol A; compared with petroleum-based polyaryletherketone, the bio-based polyaryletherketone synthesized by polymerizing the combination of the soybean flavone and the conventional diphenol monomer with the fluoroketone has the mechanical property equivalent to that of the existing petroleum-based polyaryletherketone, has certain degradability, and can replace the existing petroleum-based polyaryletherketone to be applied to profiles such as composite materials, films, plate-rod tubes and the like.

Description

Technical Field

[0001] This invention relates to the field of polyaryletherketone technology, specifically to a bio-based polyaryletherketone and its preparation method. Background Technology

[0002] Polyaryletherketone (PAEK) is a class of crystalline polymers composed of phenylene rings linked by oxygen bridges (ether bonds) and carbonyl groups (ketones). Depending on the order and ratio of ether bonds, ketone groups, and benzene rings in the molecular chain, many different polymers can be formed. The main varieties include polyetheretherketone (PEEK), polyetherketone (PEK), polyetherketoneketone (PEKK), polyetheretherketoneketone (PEEKK), and polyetherketoneetherketoneketone (PEKEKK). The presence of rigid benzene rings in the PAEK molecular structure gives it excellent high-temperature performance, mechanical properties, electrical insulation, radiation resistance, and chemical resistance, making it a highly versatile engineering plastic. It is widely used in defense, military, electronics, and medical fields.

[0003] In recent years, researchers have synthesized bio-based PAEK using fumaric acid, 2,5-furandicarboxylic acid, 4-aminocinnamic acid, isosorbide, lignin derivatives, adenine, and inositol. However, due to the conflict between structural design and performance requirements, existing bio-based PAEK materials struggle to simultaneously achieve properties such as mechanical strength and heat resistance. Secondly, existing bio-based PAEK materials exhibit low monomer reactivity, particularly bio-based alcohol monomers such as isosorbide and inositol, which require strong bases like sodium hydride for polymerization. This low monomer reactivity can lead to low product yield and purity. Summary of the Invention

[0004] To address the aforementioned technical problems, a bio-based polyarylether ketone and its preparation method are provided. This invention utilizes a highly reactive bio-based dihydroxy monomer to synthesize a bio-based polyarylether ketone, resulting in a product with superior thermal stability and mechanical properties.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0006] A bio-based polyaryletherketone, wherein the repeating unit comprises a first structural unit and a second structural unit;

[0007] The first structural unit has the following structure:

[0008]

[0009] The second structural unit has the following structure:

[0010]

[0011] Ar1 is selected from one of the following groups:

[0012]

[0013] The molar percentage of the first structural unit is 0.5%-99.5%.

[0014] A method for preparing a bio-based polyarylether ketone includes the following steps:

[0015] 4,4'-difluorobenzophenone monomer and bisphenol monomer are dissolved in a salting agent in a reaction solvent, and then heated to carry out an aromatic nucleophilic condensation reaction to obtain a bio-based polyarylether ketone.

[0016] The diphenol monomer is selected from one or more of hydroquinone, resorcinol, 4,4'-biphenyl, 4,4'-dihydroxybenzophenone, and bisphenol A, combined with soy isoflavones.

[0017] Furthermore, the molar ratio of the 4,4'-difluorobenzophenone monomer to the diphenol monomer is 1-1.1:1; the molar percentage of the soybean isoflavone in the diphenol monomer is 1%-99%.

[0018] Furthermore, the aromatic nucleophilic condensation reaction process is as follows: the temperature is raised to the first reaction temperature and held for 30-60 minutes, then the temperature is raised to the second reaction temperature and held for 2-6 hours.

[0019] The first reaction temperature is 220℃-260℃; the second reaction temperature is 300-320℃.

[0020] Furthermore, after heating to the second reaction temperature and maintaining the temperature for 2-4 hours, a molecular weight regulator is added while maintaining the reaction temperature to carry out a chain growth reaction for 0.5-1 hours; the molecular weight regulator is selected from one or more of hydroquinone, resorcinol, 4,4'-biphenyl, 4,4'-dihydroxybenzophenone, bisphenol A, and soybean isoflavone; the amount of the molecular weight regulator is 0.5%-1% of the molar amount of the diphenol monomer.

[0021] Furthermore, after heating to the second reaction temperature and maintaining the temperature for 2-4 hours, a molecular weight regulator is added to carry out a chain growth reaction for 0.5-1 hour while maintaining the reaction temperature, and a capping agent is added to carry out a capping reaction for 0.5-1 hour. The capping agent is selected from 4,4'-difluorobenzophenone and / or fluorobenzene-based capping agents (such as those described in CN116023248A), and the amount of the capping agent is 1%-3% of the molar amount of the 4,4'-difluorobenzophenone monomer.

[0022] Furthermore, the salt-forming agent is anhydrous sodium carbonate and / or anhydrous potassium carbonate;

[0023] The reaction solvent is selected from one of diphenyl sulfone, sulfolane, N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, and dimethyl sulfoxide.

[0024] Furthermore, the amount of the salt-forming agent is 50%-70% of the total molar amount of the 4,4'-difluorobenzophenone monomer and the bisphenol monomer; the amount of the reaction solvent is 25%-35% of the mass percentage of theoretical yield / (theoretical yield + reaction solvent).

[0025] Furthermore, the reaction solvent is diphenyl sulfone.

[0026] Furthermore, the order of addition is as follows: first, the reaction solvent is heated to 120-140°C, and after the reaction solvent is dissolved, the 4,4'-difluorobenzophenone monomer and the salting agent are added in sequence. The temperature is then raised to 140-170°C, and then the bisphenol monomer is added. After it is completely dissolved, the temperature is raised to carry out the aromatic nucleophilic condensation reaction.

[0027] After the aromatic nucleophilic condensation reaction is completed, the reactants are poured into a poor solvent to precipitate the reaction products. The reaction products are then crushed and washed multiple times.

[0028] Beneficial technical effects: This invention uses a combination of soybean isoflavones and conventional diphenol monomers to polymerize with fluoroketones to synthesize bio-based polyarylether ketones. Compared with petroleum-based polyarylether ketones, the bio-based polyarylether ketones synthesized in this invention have comparable mechanical properties to petroleum-based polyarylether ketones and have a certain degree of biodegradability. Detailed Implementation

[0029] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit the present invention or its application or use. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0030] Unless otherwise specifically stated, the numerical values ​​set forth in these embodiments do not limit the scope of the invention. Techniques and methods known to those skilled in the art may not be discussed in detail, but where appropriate, such techniques and methods should be considered part of the specification. In all examples shown and discussed herein, any specific values ​​should be interpreted as merely exemplary and not as limitations. Therefore, other examples of exemplary embodiments may have different values. It should be noted that values ​​expressed, for example, as "within the range of ab" or "between the range of ab," do not include the endpoint values ​​a and b; values ​​expressed as "for ab," "is ab," or "ab" include the endpoint values ​​a and b.

[0031] Furthermore, it should be noted that the use of terms such as "first" and "second" to define unit structures or reaction temperatures is merely for the purpose of distinguishing between different structures or reaction steps. Unless otherwise stated, these terms have no special meaning and therefore should not be construed as limiting the scope of protection of this invention.

[0032] Experimental methods not specified in the following examples are generally performed according to national standards; if there is no corresponding national standard, they are performed according to general standard requirements or general methods.

[0033] The molecular structures of soybean isoflavones used in the following process are as follows:

[0034] Purchased from Saen Chemical Technology (Shanghai) Co., Ltd.

[0035] Example 1

[0036] A bio-based polyaryletherketone has the following chemical structure:

[0037]

[0038] The preparation method of the above-mentioned bio-based polyarylether ketone with the chemical structure includes the following steps:

[0039] In a 1000 mL four-necked flask equipped with a mechanical stirrer, reflux condenser, nitrogen inlet, and thermometer, under nitrogen protection, stirring was started, and 350 g of diphenyl sulfone was added. The temperature was gradually raised to 140 °C. After the diphenyl sulfone was completely dissolved, 110.95 g (0.51 mol) of 4,4'-difluorobenzophenone and 60.00 g (0.57 mol) of anhydrous sodium carbonate (200 mesh) were added sequentially. Then, the temperature was raised to 160 °C, and 27.53 g (0.25 mol) of hydroquinone and 63.56 g (0.25 mol) of soybean isoflavone were added. After complete dissolution, the temperature was raised to 250 °C and reacted for 1 h. The temperature was then raised to 310 °C and reacted for another 3 h to obtain a low molecular weight... A certain amount of bio-based polyaryletherketone was prepared; then 0.50 g of hydroquinone was added, and the reaction was continued at 310 °C for 30 minutes to allow the bio-based polyaryletherketone molecular chain to grow; finally, 2.00 g of 4,4'-difluorobenzophenone was added as a capping agent, and the bio-based polyaryletherketone was capped at 310 °C for 30 minutes. The material was then poured into cold distilled water to obtain a white block. The white block was crushed with a pulverizer, washed five times with acetone to remove solvent, unreacted capping agent, and raw materials, and washed five times with distilled water to remove inorganic salts generated in the reaction, resulting in a white solid. After drying, bio-based p-phenylene polyaryletherketone with a water content of less than 0.5 wt% was obtained (yield 98.1 wt%).

[0040] Example 2

[0041] A bio-based polyaryletherketone has the following chemical structure:

[0042]

[0043] The preparation method of the above-mentioned bio-based polyarylether ketone with the chemical structure includes the following steps:

[0044] In a 1000 mL four-necked flask equipped with a mechanical stirrer, reflux condenser, nitrogen inlet, and thermometer, under nitrogen protection, stirring was started, and 350 g of diphenyl sulfone was added. The temperature was gradually raised to 140 °C. After the diphenyl sulfone was completely dissolved, 110.95 g (0.51 mol) of 4,4'-difluorobenzophenone and 60.00 g (0.57 mol) of anhydrous sodium carbonate (200 mesh) were added sequentially. Then, the temperature was raised to 160 °C, and 27.53 g (0.25 mol) of resorcinol and 63.56 g (0.25 mol) of soybean isoflavones were added. After complete dissolution, the temperature was raised to 250 °C and reacted for 1 h. The temperature was then raised to 310 °C and reacted for another 3 h to obtain low molecular weight biological... Bio-based m-phenylene ether ketone was prepared by adding 1g of soybean isoflavone and continuing the reaction at 310℃ for 30 minutes to promote the growth of the bio-based m-phenylene ether ketone molecular chain. Finally, 2.00g of 4,4'-difluorobenzophenone was added as a capping agent, and the bio-based m-phenylene ether ketone was capped at 310℃ for another 30 minutes. The material was then poured into cold distilled water to obtain a white block. The white block was crushed with a pulverizer, washed five times with acetone to remove solvent, unreacted capping agent, and raw materials, and washed five times with distilled water to remove inorganic salts generated in the reaction, resulting in a white solid. After drying, bio-based m-phenylene ether ketone with a water content of less than 0.5wt% (yield 98.3wt%) was obtained.

[0045] Example 3

[0046] A bio-based polyaryletherketone has the following chemical structure:

[0047]

[0048] The preparation method of the above-mentioned bio-based polyarylether ketone with the chemical structure includes the following steps:

[0049] In a 1000 mL four-necked flask equipped with a mechanical stirrer, reflux condenser, nitrogen inlet, and thermometer, under nitrogen protection, stirring was started, and 400 g of diphenyl sulfone was added. The temperature was gradually raised to 140 °C. After the diphenyl sulfone was completely dissolved, 110.95 g (0.51 mol) of 4,4'-difluorobenzophenone and 60.00 g (0.57 mol) of anhydrous sodium carbonate (200 mesh) were added sequentially. Then, the temperature was raised to 160 °C, and 46.55 g (0.25 mol) of 4,4'-biphenylhydroquinone and 63.56 g (0.25 mol) of soybean isoflavones were added. After complete dissolution, the temperature was raised to 250 °C and reacted for 1 h. The temperature was then raised to 310 °C and reacted for another 3 h to obtain a low molecular weight biomass. Bio-based biphenyl polyaryletherketone (BPA) was prepared by adding 0.50 g hydroquinone and continuing the reaction at 310 °C for 30 minutes to promote the growth of the BPA molecular chain. Finally, 2.00 g of 4,4'-difluorobenzophenone was added as a capping agent, and the reaction was continued at 310 °C for another 30 minutes. The material was then poured into cold distilled water to obtain a white lumpy substance. This substance was crushed and washed five times with acetone to remove solvent, unreacted capping agent, and raw materials. The mixture was then washed five times with distilled water to remove inorganic salts generated during the reaction, yielding a white solid. After drying, a BPA with a water content of less than 0.5 wt% (yield 98.1 wt%) was obtained.

[0050] Example 4

[0051] A bio-based polyaryletherketone has the following chemical structure:

[0052]

[0053] The preparation method of the above-mentioned bio-based polyarylether ketone with the chemical structure includes the following steps:

[0054] In a 1000 mL four-necked flask equipped with a mechanical stirrer, reflux condenser, nitrogen inlet, and thermometer, under nitrogen protection, stirring was started, and 450 g of diphenyl sulfone was added. The temperature was gradually raised to 140 °C. After the diphenyl sulfone was completely dissolved, 93.39 g (0.43 mol) of 4,4'-difluorobenzophenone and 55.11 g (0.52 mol) of anhydrous sodium carbonate (200 mesh) were added sequentially. Then, the temperature was raised to 160 °C and 42.85 g (0.2 mol) of anhydrous sodium carbonate (200 mesh) was added. 0.20 mol of 4,4'-dihydroxybenzophenone and 50.85 g of soybean isoflavone were completely dissolved and reacted at 250 °C for 1 h, then the temperature was increased to 310 °C for 3 h to obtain low molecular weight bio-based polyarylether ketone. Then, 1.0 g of 4,4'-dihydroxybenzophenone or 1.0 g of soybean isoflavone was added, and the reaction was continued at 310 °C for 30 min to allow the bio-based polyarylether ketone molecular chain to grow. Finally, 2.00 g of... Using 4,4'-difluorobenzophenone as a capping agent, the bio-based polyarylether ketone was subjected to a capping reaction at 310°C for 30 min. The material was then poured into cold distilled water to obtain a white lumpy substance. The white lumpy substance was crushed with a pulverizer and washed five times with acetone to remove the solvent, unreacted capping agent, and raw materials. The mixture was then washed five times with distilled water to remove the inorganic salts generated in the reaction, resulting in a white solid. After drying, the bio-based polyarylether ketone with a water content of less than 0.5 wt% (yield 98.2 wt%) was obtained.

[0055] Example 5

[0056] A bio-based polyaryletherketone has the following chemical structure:

[0057]

[0058] The preparation method of the above-mentioned bio-based polyarylether ketone with the chemical structure includes the following steps:

[0059] In a 1000 mL four-necked flask equipped with a mechanical stirrer, reflux condenser, nitrogen inlet, and thermometer, under nitrogen protection, stirring was started, and 450 g of diphenyl sulfone was added. The temperature was gradually raised to 140 °C. After the diphenyl sulfone was completely dissolved, 93.39 g (0.43 mol) of 4,4'-difluorobenzophenone and 55.11 g (0.52 mol) of anhydrous sodium carbonate (200 mesh) were added sequentially. Then, the temperature was raised to 160 °C, and 45.66 g (0.20 mol) of bisphenol A and 50.85 g of soybean isoflavone (0.20 mol) were added. After complete dissolution, the temperature was raised to 250 °C and reacted for 1 h. The temperature was then raised to 310 °C and reacted for another 3 h to obtain a low molecular weight bio-based diphenyl sulfone. Phenolic A-type polyarylether ketone was prepared; then 1.0 g of soybean isoflavone was added, and the reaction was continued at 310 °C for 30 minutes to increase the molecular chain of the bio-based bisphenol A-type polyarylether ketone; finally, 2.00 g of 4,4'-difluorobenzophenone was added as a capping agent, and the bio-based polyarylether ketone was capped at 310 °C for 30 minutes. The material was then poured into cold distilled water to obtain a white block. The white block was crushed with a pulverizer, washed five times with acetone to remove solvent, unreacted capping agent, and raw materials, and washed five times with distilled water to remove inorganic salts generated in the reaction, resulting in a white solid. After drying, bio-based bisphenol A-type polyarylether ketone with a water content of less than 0.5 wt% (yield 97.8 wt%) was obtained.

[0060] Comparative Example 1

[0061] The preparation process in this case is the same as in Example 1, except that soybean isoflavones were not added and the amount of hydroquinone was adjusted to 0.5 mol, thus obtaining PEEK with the conventional configuration.

[0062] Test case

[0063] Performance tests were conducted on the above embodiments and comparative examples, and the results are shown in Table 1.

[0064] Table 1 Performance of Examples and Comparative Examples

[0065] Tensile strength tensile modulus Elongation at break Bending strength Flexural modulus unit MPa GPa ％ MPa GPa Test Standards ISO 527 ISO 527 ISO 527 ISO 178 ISO 178 Comparative Example 1 95 3.67 25 165 3.8 Example 1 90.9 3.82 24.84 156.56 3.66 Example 2 86.87 3.21 55.24 128.35 3.08 Example 3 102.25 3.56 54.26 145.66 3.31 Example 4 113.87 4.01 25.19 178.65 3.61 Example 5 84.23 3.12 56.88 123.48 3.12

[0066] This invention uses a combination of soybean isoflavones and conventional diphenol monomers to polymerize with fluoroketones to synthesize a bio-based polyarylether ketone. Compared with petroleum-based polyarylether ketones, the mechanical properties are comparable to those of existing petroleum-based polyarylether ketones, and it also has a certain degree of biodegradability.

[0067] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A bio-based polyaryletherketone, characterized in that, Its repeating units include a first structural unit and a second structural unit; The first structural unit has the following structure: The second structural unit has the following structure: Ar1 is selected from one of the following groups: The molar percentage of the first structural unit is 0.5%-99.5%.

2. A method for preparing a bio-based polyaryletherketone, characterized in that, Includes the following steps: 4,4'-difluorobenzophenone monomer and bisphenol monomer are dissolved in a salting agent in a reaction solvent, and then heated to carry out an aromatic nucleophilic condensation reaction to obtain a bio-based polyarylether ketone. The diphenol monomer is selected from one or more of hydroquinone, resorcinol, 4,4'-biphenyl, 4,4'-dihydroxybenzophenone, and bisphenol A, combined with soy isoflavones.

3. The method for preparing a bio-based polyaryletherketone according to claim 2, characterized in that, The molar ratio of the 4,4'-difluorobenzophenone monomer to the diphenol monomer is 1-1.1:1; the molar percentage of the soybean isoflavone in the diphenol monomer is 1%-99%.

4. The method for preparing a bio-based polyarylether ketone according to claim 3, characterized in that, The aromatic nucleophilic condensation reaction process is as follows: heat to the first reaction temperature and hold for 30-60 minutes, then heat to the second reaction temperature and hold for 2-6 hours. The first reaction temperature is 220℃-260℃; the second reaction temperature is 300-320℃.

5. The method for preparing a bio-based polyarylether ketone according to claim 4, characterized in that, After heating to the second reaction temperature and holding the reaction at that temperature for 2-4 hours, a molecular weight regulator is added while maintaining the reaction temperature to initiate a chain growth reaction for 0.5-1 hours. The molecular weight regulator is selected from one or more of hydroquinone, resorcinol, 4,4'-biphenyl, 4,4'-dihydroxybenzophenone, bisphenol A, and soybean isoflavones. The amount of the molecular weight regulator used is 0.5%-1% of the molar amount of the diphenol monomer.

6. The method for preparing a bio-based polyaryletherketone according to claim 4, characterized in that, After heating to the second reaction temperature and holding the reaction at that temperature for 2-4 hours, a molecular weight regulator is added while maintaining the reaction temperature to carry out a chain growth reaction for 0.5-1 hour. Then, while maintaining the reaction temperature, a capping agent is added to carry out a capping reaction for 0.5-1 hour. The capping agent is selected from 4,4'-difluorobenzophenone and / or fluorobenzene-based capping agents, and the amount of the capping agent is 1%-3% of the molar amount of the 4,4'-difluorobenzophenone monomer.

7. A method for preparing a bio-based polyarylether ketone according to any one of claims 2-6, characterized in that, The salt-forming agent is anhydrous sodium carbonate and / or anhydrous potassium carbonate; The reaction solvent is selected from one of diphenyl sulfone, sulfolane, N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, and dimethyl sulfoxide.

8. The method for preparing a bio-based polyarylether ketone according to claim 7, characterized in that, The amount of the salt-forming agent is 50%-70% of the total molar amount of the 4,4'-difluorobenzophenone monomer and the bisphenol monomer; the amount of the reaction solvent is 25%-35% of the mass percentage of theoretical yield / (theoretical yield + reaction solvent).

9. The method for preparing a bio-based polyarylether ketone according to claim 7, characterized in that, The reaction solvent is diphenyl sulfone.

10. The method for preparing a bio-based polyarylether ketone according to claim 9, characterized in that, The order of addition is as follows: first, heat the reaction solvent to 120-140°C, and after the reaction solvent is dissolved, add the 4,4'-difluorobenzophenone monomer and the salting agent in sequence, continue to heat to the range of 140-170°C, and then add the bisphenol monomer. After it is completely dissolved, heat up to carry out the aromatic nucleophilic condensation reaction. After the aromatic nucleophilic condensation reaction is completed, the reactants are poured into a poor solvent to precipitate the reaction products. The reaction products are then crushed and washed multiple times.

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