Fluorine-containing semi-crystalline polyaryletherketone, preparation method and application thereof, polymer film material and application thereof

Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to fluorine-containing semi-crystalline polyaryletherketone, a preparation method and application thereof, a polymer film material and application thereof. The fluorine-containing semi-crystalline polyaryletherketone provided by the invention has a structure as shown in a formula I, wherein X includes, or; a is any integer from 1 to 3, and n is the degree of polymerization. According to the fluorine-containing semi-crystalline polyaryletherketone provided by the invention, a fluorine-containing group is introduced, and the fluorine-containing semi-crystalline polyaryletherketone has a symmetrical structure, has relatively high crystallinity and relatively low surface energy, and also has excellent mechanical properties, so that the application range of the fluorine-containing semi-crystalline polyaryletherketone is greatly expanded.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a fluorinated semi-crystalline polyarylether ketone and its preparation method and application, as well as polymer membrane materials and their applications. Background Technology

[0002] Polyaryletherketone (PAEK) is a class of aromatic crystalline polymers linked by ether bonds, ketone groups and phenylene groups. It has attracted much attention due to its high heat resistance, good dielectric properties, chemical corrosion resistance, radiation resistance and excellent mechanical properties, and is widely used in aerospace, petroleum industry, machinery, electronics, nuclear energy and defense industry.

[0003] However, when polyaryletherketone (PAGE) materials are used in biomedical implants, their high surface energy easily adsorbs proteins, triggering foreign body reactions and affecting their effectiveness. To improve their surface properties, existing technologies often achieve surface energy modulation by introducing fluorine-containing groups into the polymer backbone or side chains. However, conventional copolymerization modification methods (such as random copolymerization) often lead to the destruction of molecular chain structure symmetry when increasing the fluorine content, causing a sharp decrease in the material's crystallinity (usually below 10%), or even causing it to transform into an amorphous polymer, significantly reducing its mechanical properties. Summary of the Invention

[0004] In view of this, the present invention provides a fluorinated semi-crystalline polyaryletherketone, its preparation method and application, and a polymer film material and its application. The fluorinated semi-crystalline polyaryletherketone provided by the present invention has low surface energy and high crystallinity, as well as excellent mechanical properties and low coefficient of friction.

[0005] To solve the above-mentioned technical problems, the present invention provides a fluorinated semi-crystalline polyarylether ketone having the structure shown in Formula I: Formula I; Where X includes , or ; a is any integer from 1 to 3, and n is the degree of aggregation.

[0006] Preferably, the fluorinated semi-crystalline polyarylether ketone has a structure shown in any one of formulas II to VII: .

[0007] Preferably, the fluorinated semi-crystalline polyaryletherketone has an Ubbelohde viscosity of 0.32~0.96 dL / g, a glass transition temperature of 159~178℃, a melting point of 315~357℃, a crystallinity of 20~35%, and a surface energy of 30.3~36.9 mJ / m².2 .

[0008] The present invention also provides a method for preparing the fluorinated semi-crystalline polyarylether ketone described in the above technical solution, comprising the following steps: 1,4'-bis(fluorobenzoyl)benzene, a high-boiling-point solvent, compound 1, an alkali metal salt-forming agent and a first dehydrating agent are mixed and subjected to a first polymerization reaction to obtain an oligomer; The system after the first polymerization reaction, hexafluorobisphenol A, and the second dehydrating agent are mixed and then subjected to a second polymerization reaction to obtain the fluorinated semi-crystalline polyarylether ketone. The compound 1 is X includes , or .

[0009] Preferably, the high-boiling-point solvent includes diphenyl sulfone or sulfolane; The alkali metal salt-forming agent includes anhydrous potassium carbonate and / or anhydrous sodium carbonate; The first and second water-removing agents independently include toluene or xylene.

[0010] Preferably, the molar ratio of 1,4'-bis(fluorobenzoyl)benzene to compound 1 is (10~12.5):(4~8); The mass ratio of the total mass of the 1,4'-bis(fluorobenzoyl)benzene and compound 1 to the mass of the high-boiling solvent is (38~50):180; The molar ratio of the 1,4'-bis(fluorobenzoyl)benzene to the alkali metal salt-forming agent is (1~1.3):(1.1~1.3); The mass ratio of the high-boiling-point solvent to the volume ratio of the first dehydrating agent is 5g:(2~5)mL; The first polymerization reaction is a first gradient heating reaction, which includes the following steps in sequence: heating to a first reaction temperature to carry out a first reaction, heating to a second reaction temperature to carry out a second reaction, and heating to a third reaction temperature to carry out a third reaction. The temperature of the first reaction is 160~180℃, and the reaction time is 1~3h; the temperature of the second reaction is 210~230℃, and the reaction time is 0.8~1.2h; the temperature of the third reaction is 240~260℃, and the reaction time is 0.8~1.2h.

[0011] Preferably, the molar ratio of 1,4'-bis(fluorobenzoyl)benzene to hexafluorobisphenol A is (1~1.3):(0.3~0.5); The volume ratio of the second water-removing agent to the mass ratio of the high-boiling-point solvent is (2~5) mL: 5g; The second polymerization reaction is a second gradient heating reaction, which includes the following steps in sequence: heating to a fourth reaction temperature to carry out the fourth reaction, heating to a fifth reaction temperature to carry out the fifth reaction, heating to a sixth reaction temperature to carry out the sixth reaction, and heating to a seventh reaction temperature to carry out the seventh reaction. The temperature of the fourth reaction is 160~180℃, and the time of the fourth reaction is 1.5~2.5h; the temperature of the fifth reaction is 220~240℃, and the time of the fifth reaction is 0.8~1.2h; the temperature of the sixth reaction is 240~260℃, and the time of the sixth reaction is 0.8~1.2h; the temperature of the seventh reaction is 270~290℃, and the time of the seventh reaction is 3~5h.

[0012] Preferably, the process further includes post-processing of the system after the second polymerization reaction, the post-processing including: solid-liquid separation after solid precipitation, and sequentially subjecting the solid obtained from the solid-liquid separation to solid pulverization, primary washing, secondary washing and drying.

[0013] The present invention also provides a polymer membrane material, which is prepared from the fluorinated semi-crystalline polyaryletherketone described in the above technical solution or the fluorinated semi-crystalline polyaryletherketone prepared by the preparation method described in the above technical solution.

[0014] The present invention also provides the application of the fluorinated semi-crystalline polyaryletherketone (PAGE) described in the above technical solution or the fluorinated semi-crystalline PAGE prepared by the preparation method described in the above technical solution or the polymer membrane material described in the above technical solution in the preparation of biomedical implants, high-frequency electronic substrates, high-performance separation membranes, precision manufacturing demolding and harsh industrial anti-sticking.

[0015] This invention provides a fluorinated semi-crystalline polyarylether ketone having the structure shown in Formula I: Formula I; where X includes , or ; a is any integer from 1 to 3, and n is the degree of polymerization. This invention introduces fluorinated groups into the molecular structure of fluorinated semi-crystalline polyaryletherketones (PAGEs). On the one hand, this reduces its surface energy, giving it excellent hydrophobic properties and low surface energy characteristics, and facilitating the material's shedding and formation of a transfer film in a frictional environment, effectively reducing the friction coefficient of the fluorinated semi-crystalline PAGEs. On the other hand, the fluorinated semi-crystalline PAGEs provided by this invention have a symmetrical structure, overcoming the problem of significantly reduced solvent resistance caused by the addition of more fluorinated groups to PAGEs, effectively maintaining its crystallinity and modulus, and improving its mechanical strength, heat resistance, and wear resistance. The fluorinated semi-crystalline PAGEs provided by this invention have low surface energy characteristics (30.3~36.9 mJ / m). 2Compared to traditional polyaryletherketones, it has superior hydrophobicity (92.5°~101°); and its coefficient of friction is 0.40~0.44, with significantly reduced friction coefficient and wear rate, showing excellent self-lubricating effect.

[0016] The present invention provides a method for preparing a fluorinated semi-crystalline polyarylether ketone, comprising the following steps: mixing 1,4'-bis(fluorobenzoyl)benzene, a high-boiling-point solvent, compound 1, an alkali metal salt-forming agent, and a first dehydrating agent, and then carrying out a first polymerization reaction to obtain an oligomer; mixing the system after the first polymerization reaction, hexafluorobisphenol A, and a second dehydrating agent, and then carrying out a second polymerization reaction to obtain the fluorinated semi-crystalline polyarylether ketone; wherein compound 1 is... X includes , or This invention employs a stepwise polymerization method to form a regular and ordered molecular structure, selecting different structural units to adjust the structural symmetry of its molecular chain segments, thereby reducing its surface properties while improving its crystallinity. Attached Figure Description

[0017] Figure 1 The infrared absorption spectra of the fluorinated semi-crystalline polyaryletherketones prepared in Examples 2, 4, and 6 are shown. Figure 2 The TGA images are of the fluorinated semi-crystalline polyaryletherketone powders prepared in Examples 2, 4, and 6. Figure 3 The following are DSC images of the fluorinated semi-crystalline polyaryletherketone powders prepared in Examples 2, 4, and 6; Figure 4 The XRD patterns of the fluorinated semi-crystalline polyaryletherketone powders prepared in Examples 2, 4, and 6 are shown below. Figure 5 The stress-strain curves of the polymer film materials prepared in Examples 2, 4, and 6 are shown. Figure 6 The DMA curves of the fluorinated semi-crystalline polyaryletherketone powders prepared in Examples 2, 4, and 6 are shown. Figure 7 The friction curves of the polymer film materials prepared in Examples 2, 4, 6 and Comparative Examples 1-2 are shown at room temperature (25°C). Figure 8 The graph shows a comparison of the surface energy of the polymer film materials prepared in Examples 1-6 and Comparative Examples 1-2. Detailed Implementation

[0018] This invention provides a fluorinated semi-crystalline polyarylether ketone having the structure shown in Formula I: Formula I; Where X includes , or .

[0019] In this invention, a is any integer from 1 to 3, specifically 1, 2 or 3; n is the degree of aggregation.

[0020] As a specific embodiment of the present invention, the fluorinated semi-crystalline polyarylether ketone may have the structure shown in any one of formulas II to VII: .

[0021] In one specific embodiment of the present invention, the specific viscosity of the fluorinated semi-crystalline polyarylether ketone can be 0.32~0.96 dL / g, or 0.43~0.92 dL / g, specifically 0.75 dL / g, 0.68 dL / g, or 0.70 dL / g. The glass transition temperature of the fluorinated semi-crystalline polyaryletherketone can be 159~178℃, specifically 160℃, 163℃, 165℃, 168℃, 170℃ or 175℃; the melting point of the fluorinated semi-crystalline polyaryletherketone can be 315~357℃, specifically 320℃, 325℃, 326℃, 330℃, 335℃, 340℃, 345℃, 350℃ or 355℃; the crystallinity of the fluorinated semi-crystalline polyaryletherketone can be 20~35%, specifically 21%, 25%, 27%, 30% or 34%; the surface energy of the fluorinated semi-crystalline polyaryletherketone can be 30~37mJ / m 2 Specifically, it can be expressed as 30.3 mJ / m 2 31.4 mJ / m 2 32.3 mJ / m 2 33mJ / m 2 36.1 mJ / m 2 36.7mJ / m 2 Or 36.9 mJ / m 2 The water contact angle of the fluorinated semi-crystalline polyaryletherketone can be 92.5~101°, specifically 92.8°, 93.2°, 99.3° or 100.5°; the ethylene glycol contact angle of the fluorinated semi-crystalline polyaryletherketone can be 59~70.7°, specifically 59.2°, 59.5°, 65°, 68.6° or 69.2°.

[0022] The present invention also provides a method for preparing the fluorinated semi-crystalline polyarylether ketone described in the above technical solution, comprising the following steps: 1,4'-bis(fluorobenzoyl)benzene, a high-boiling-point solvent, compound 1, an alkali metal salt-forming agent and a first dehydrating agent are mixed and subjected to a first polymerization reaction to obtain an oligomer; The system after the first polymerization reaction, hexafluorobisphenol A, and the second dehydrating agent are mixed and then subjected to a second polymerization reaction to obtain the fluorinated semi-crystalline polyarylether ketone. The compound 1 is X includes , or .

[0023] This invention involves mixing 1,4'-bis(fluorobenzoyl)benzene, a high-boiling-point solvent, compound 1, an alkali metal salt-forming agent, and a first dehydrating agent, followed by a first polymerization reaction to obtain an oligomer. In one specific embodiment of this invention, the high-boiling-point solvent may include diphenyl sulfone or sulfolane; the alkali metal salt-forming agent may include anhydrous potassium carbonate and / or anhydrous sodium carbonate, specifically a mixture of anhydrous potassium carbonate and anhydrous sodium carbonate, or anhydrous potassium carbonate or anhydrous sodium carbonate; in this invention, when the alkali metal salt-forming agent is anhydrous potassium carbonate and anhydrous sodium carbonate, the molar ratio of anhydrous potassium carbonate to anhydrous sodium carbonate may be 1:(7~9), or 1:(7.7~9). In another specific embodiment of this invention, the first dehydrating agent may include toluene or xylene.

[0024] In one specific embodiment of the present invention, the molar ratio of 1,4'-bis(fluorobenzoyl)benzene to compound 1 can be (10~12.5):(4~8), specifically 10.1:5, 12.1:4, 12.1:8, 10.8:7.2, or 10.6:7; the mass ratio of the total mass of 1,4'-bis(fluorobenzoyl)benzene and compound 1 to the mass of the high-boiling-point solvent can be (38~50):180, specifically 38.06:180, 47.87:180, 41.86:180, or 48... 0.21:180, 43.26:180, or 49.18:180; the molar ratio of the 1,4'-bis(fluorobenzoyl)benzene and the alkali metal salt-forming agent can be (1~1.3):(1.1~1.3), specifically 1.01:1.20, 1.21:1.25, 1.08:1.30, or 1.06:1.26; the mass ratio of the high-boiling-point solvent to the volume ratio of the first dehydrating agent can be 5g:(2~5)mL, specifically 5g:2mL, 5g:3mL, 5g:4mL, or 5g:5mL.

[0025] The present invention has no special requirements for the mixing, as long as the mixing is uniform.

[0026] In one specific embodiment of the present invention, the first polymerization reaction can be a first gradient heating reaction, which can sequentially include the following steps: heating to a first reaction temperature for a first reaction, heating to a second reaction temperature for a second reaction, and heating to a third reaction temperature for a third reaction; the temperature of the first reaction can be 160~180℃, specifically 160℃, 165℃, 170℃, 175℃ or 180℃; the time of the first reaction can be 1~3 hours, specifically... The reaction time can be 1 hour, 1.5 hours, 2 hours, 2.5 hours, or 3 hours; the temperature of the second reaction can be 210~230℃, specifically 210℃, 215℃, 220℃, 225℃, or 230℃; the reaction time can be 0.8~1.2 hours, specifically 1 hour; the temperature of the third reaction can be 240~260℃, specifically 240℃, 245℃, 250℃, 255℃, or 260℃; the reaction time can be 0.8~1.2 hours, specifically 1 hour.

[0027] In one specific embodiment of the present invention, the first polymerization reaction can be carried out under a protective atmosphere, which may include argon or nitrogen. By conducting the first polymerization reaction under a protective atmosphere, the present invention can avoid the oxidation reaction between oxygen in the air and the reactants, leading to other side reactions, caused by the high temperatures during the reaction process.

[0028] In one specific embodiment of the present invention, the process may further include: cooling the system after the first polymerization reaction; the cooled temperature may be 145~155℃, specifically 150℃. The present invention may further increase the temperature after cooling to carry out a second polymerization reaction.

[0029] After obtaining the oligomer, the present invention mixes the first polymerization reaction system, hexafluorobisphenol A, and the second dehydrating agent and carries out a second polymerization reaction to obtain the fluorinated semi-crystalline polyarylether ketone. In one specific embodiment of the present invention, the second dehydrating agent may include toluene or xylene. In another specific embodiment of the present invention, the molar ratio of 1,4'-bis(fluorobenzoyl)benzene to hexafluorobisphenol A may be (1~1.3):(0.3~0.5), specifically 1.01:0.5, 1.21:0.4, 1.08:0.36, or 1.06:0.35; the volume ratio of the second dehydrating agent to the mass ratio of the high-boiling-point solvent may be (2~5) mL:5g, specifically 2 mL:5g, 3 mL:5g, 4 mL:5g, or 5 mL:5g.

[0030] In one specific embodiment of the present invention, the second polymerization reaction can be a second gradient heating reaction, which can sequentially include the following steps: heating to a fourth reaction temperature for a fourth reaction, heating to a fifth reaction temperature for a fifth reaction, heating to a sixth reaction temperature for a sixth reaction, and heating to a seventh reaction temperature for a seventh reaction; the temperature of the fourth reaction can be 160~180℃, specifically 160℃, 165℃, 170℃, 175℃ or 180℃; the time of the fourth reaction can be 1.5~2.5h, specifically 2h; the temperature of the fifth reaction can be 220~240℃, specifically... The temperatures for the fifth reaction are 220℃, 225℃, 230℃, 235℃, or 240℃; the reaction time for the sixth reaction can be 0.8~1.2h, specifically 1h; the temperature for the sixth reaction can be 240~260℃, specifically 240℃, 245℃, 250℃, 255℃, or 260℃; the reaction time for the sixth reaction can be 0.8~1.2h, specifically 1h; the temperature for the seventh reaction can be 270~290℃, specifically 270℃, 275℃, 280℃, 285℃, or 290℃; the reaction time for the seventh reaction can be 3~5h, specifically 3h, 3.5h, 4h, 4.5h, or 5h.

[0031] In one specific embodiment of the present invention, the second polymerization reaction can be carried out under a protective atmosphere, which may include argon or nitrogen.

[0032] In this invention, the equations for the first polymerization reaction and the second polymerization reaction are shown in equation a: Formula a.

[0033] As a specific embodiment of the present invention, the system after the second polymerization reaction may be further subjected to post-processing, the post-processing including: solid-liquid separation after solid precipitation, and the solid obtained by solid-liquid separation being subjected to solid pulverization, primary washing, secondary washing and drying in sequence.

[0034] In one specific embodiment of the present invention, the solvent for the solid precipitation can be water, and the water can be deionized water; the temperature of the solvent can be room temperature, and the room temperature can be 20~35℃, or 25~30℃; the specific embodiment of the solid precipitation can be: pouring the system after the second polymerization reaction into the solvent, and the polymer precipitates.

[0035] In one specific embodiment of the present invention, the system after solid precipitation can be cooled before solid-liquid separation. The cooled temperature can be room temperature, which can be 20~30℃, specifically 25℃. The present invention does not have any special requirements for the cooling method. In another specific embodiment of the present invention, the solid-liquid separation can be filtration.

[0036] In this invention, the solid pulverization can be carried out in a high-speed pulverizer. This invention does not have special requirements on the particle size of the product after solid pulverization. This invention enables more thorough subsequent washing through pulverization.

[0037] In one specific embodiment of the present invention, the washing solvent for the first wash can be acetone, ethanol or ethyl acetate, the washing method can be heating and reflux washing, and the number of washes can be 6 to 8 times, or even 7 to 8 times.

[0038] In one specific embodiment of the present invention, the washing solvent for the secondary washing can be water, the water can be deionized water, the washing method can be heated reflux washing, and the number of washing cycles can be 5 to 6.

[0039] This invention allows for solid-liquid separation after each washing cycle, followed by a second washing of the solid product. The specific implementation of the solid-liquid separation method is not particularly demanding, as long as it achieves the desired separation. In an embodiment of this invention, the solid-liquid separation is performed using filtration.

[0040] This invention removes high-boiling-point solvents through a single wash and removes impurities, including alkali metal salts, through a second wash.

[0041] The present invention dries the solid product after secondary washing. The drying temperature can be 110~130℃ or 115~120℃; the drying time can be 22~26h or 24~25h; the drying can be carried out in a vacuum oven.

[0042] The present invention also provides a polymer membrane material, which is prepared from the fluorinated semi-crystalline polyaryletherketone described in the above technical solution or the fluorinated semi-crystalline polyaryletherketone prepared by the preparation method described in the above technical solution.

[0043] As a specific embodiment of the present invention, the method for preparing a polymer film using fluorinated semi-crystalline polyaryletherketone may include the following steps: molding the fluorinated semi-crystalline polyaryletherketone to obtain the polymer film.

[0044] In this invention, the molding process can be hot pressing, and the hot pressing temperature can be 330~400℃, specifically 340℃, 350℃, 360℃, 370℃, 380℃ or 390℃; the hot pressing pressure can be 8~12MPa, or 9~10MPa; the heat preservation and pressure holding time for hot pressing is 0.5~1.5h, or 0.8~1.2h, specifically 1h.

[0045] In one specific embodiment of the present invention, the molding process may further include annealing the molded product. In this invention, the annealing temperature can be 280~300℃, or 285~290℃; the annealing time can be 3~5 hours, specifically 4 hours. In this invention, annealing allows the uncrystallized molecular chain segments in the aggregated structure of the molded product to continue to arrange themselves in an orderly manner, improving the ordered structure of the crystalline regions and thus increasing its crystallinity.

[0046] The present invention also provides the application of the fluorinated semi-crystalline polyaryletherketone (PYG) described in the above technical solutions, or the fluorinated semi-crystalline PYG prepared by the preparation method described in the above technical solutions, or the polymer membrane material described in the above technical solutions, in the preparation of biomedical implantable devices.

[0047] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0048] In the following examples, the diphenyl sulfone structure is as follows: The structural formula of hydroquinone is: The structural formula of 1,4'-bis(fluorobenzoyl)benzene is: The structural formula of hexafluorobisphenol A (bisphenol AF) is: The structural formula of biphenyl is: The structural formula of 4,4'-dihydroxybenzophenone is: .

[0049] Example 1 A mechanical stirrer and a gas inlet with a thermometer were installed sequentially on a 500 mL three-necked flask. 180 g of diphenyl sulfone, 5.51 g (0.05 mol) of hydroquinone, 32.55 g (0.101 mol) of 1,4'-bis(fluorobenzoyl)benzene, 1.66 g of anhydrous potassium carbonate, 11.45 g of anhydrous sodium carbonate, and 72 mL of xylene were added to the reaction flask. A reflux condenser connected to the condenser was installed on the three-necked flask. The reaction system was polymerized at 170 °C under an argon atmosphere (reflux condenser) for 2 h. The reaction temperature was then increased to 220 °C and polymerized for 1 h, followed by increasing the temperature to 250 °C and polymerizing for another 1 h, then cooling to 150 °C. Finally, 16.81 g (0.05 mol) of hexafluorobisphenol A and 72 mL of xylene were added to the reaction system. Then, a water-carrying device with a reflux condenser was installed on a three-necked flask; the reaction system was polymerized at 170°C under an argon atmosphere (reflux with water) for 2 hours, the reaction temperature was raised to 230°C and polymerized for 1 hour, the temperature was raised to 250°C and polymerized for 1 hour, and the viscosity of the system was observed to increase. The temperature was raised to 280°C and polymerized for 4 hours; the reaction mixture was poured into deionized water under stirring, cooled to 25°C and filtered, the solid obtained by filtration was pulverized with a high-speed pulverizer and washed 6 times by heating and reflux with acetone, and filtered; the solid obtained by filtration was washed 5 times by heating and reflux with deionized water, and filtered; the solid obtained by filtration was placed in a vacuum oven and dried at 120°C for 24 hours; the obtained solid powder was a fluorinated semi-crystalline polyarylether ketone with the structure shown in Formula II. The obtained solid powder was hot-pressed at 340℃ and 10MPa for 1 hour and then heat-treated at 290℃ for 4 hours to obtain a polymer film material.

[0050] Example 2 A mechanical stirrer and a gas inlet with a thermometer were installed sequentially on a 500 mL three-necked flask. 180 g of diphenyl sulfone, 8.81 g (0.08 mol) of hydroquinone, 39.06 g (0.121 mol) of 1,4'-bis(fluorobenzoyl)benzene, 1.99 g of anhydrous potassium carbonate, 13.74 g of anhydrous sodium carbonate, and 72 mL of xylene were added to the reaction flask. A reflux condenser connected to the flask was installed on the three-necked flask. The reaction system was polymerized at 170 °C under an argon atmosphere (reflux condensation) for 2 h. The reaction temperature was then increased to 220 °C and polymerized for 1 h, followed by increasing the temperature to 250 °C and polymerizing for another 1 h, then cooling to 150 °C. 13.44 g (0.04 mol) of hexafluorobisphenol A and 72 mL of xylene were added to the reaction system. Next, install a water-carrying device with a reflux condenser on a three-necked flask; polymerize the reaction system at 170°C under an argon atmosphere (reflux with water) for 2 hours, then raise the reaction temperature to 230°C and polymerize for 1 hour, then raise the temperature to 250°C and polymerize for 1 hour, during which the viscosity of the system increases; finally, raise the temperature to 280°C and polymerize for 4 hours; pour the reaction mixture into deionized water while maintaining stirring, cool to 25°C, and filter; pulverize the filtered solid using a high-speed pulverizer, wash it 6 times with acetone under reflux, and filter; wash the filtered solid 5 times with deionized water under reflux, and filter; place the filtered solid in a vacuum oven at 120°C and dry for 24 hours; the obtained solid powder is a fluorinated semi-crystalline polyaryletherketone powder with the structure shown in Formula III. The obtained solid powder was hot-pressed at 340℃ and 10MPa for 1 hour, and then heat-treated at 290℃ for 4 hours to obtain a polymer film material.

[0051] Example 3 A mechanical stirrer and a gas inlet with a thermometer were installed sequentially on a 500 mL three-necked flask. 180 g of diphenyl sulfone, 9.31 g (0.05 mol) of biphenyl hydroquinone, 32.55 g (0.101 mol) of 1,4'-bis(fluorobenzoyl)benzene, 1.66 g of anhydrous potassium carbonate, 11.45 g of anhydrous sodium carbonate, and 72 mL of xylene were added to the reaction flask. A reflux condenser connected to the condenser was installed on the three-necked flask. The reaction system was polymerized at 170 °C under an argon atmosphere (reflux condenser) for 2 h. The reaction temperature was then increased to 220 °C and polymerized for 1 h, followed by increasing the temperature to 250 °C and polymerizing for another 1 h, then cooling to 150 °C. Finally, 16.81 g (0.05 mol) of hexafluorobisphenol A and 72 mL of xylene were added to the reaction system. Then, a water-carrying device with a reflux condenser was installed on a three-necked flask; the reaction system was polymerized at 170°C under an argon atmosphere (reflux with water) for 2 hours, the reaction temperature was raised to 230°C and polymerized for 1 hour, the temperature was raised to 260°C and polymerized for 1 hour, and the viscosity of the system was observed to increase. The temperature was raised to 290°C and polymerized for 4 hours; the reaction mixture was poured into deionized water under stirring, cooled to 25°C and filtered, the solid obtained by filtration was pulverized with a high-speed pulverizer and washed 6 times by heating and reflux with acetone, and filtered; the solid obtained by filtration was washed 5 times by heating and reflux with deionized water, and filtered; the solid obtained by filtration was placed in a vacuum oven and dried at 120°C for 24 hours; the obtained solid powder was a fluorinated semi-crystalline polyarylether ketone with the structure shown in Formula IV. The obtained solid powder was hot-pressed at 400℃ and 10MPa for 1 hour, and then heat-treated at 280℃ for 4 hours to obtain a polymer film material.

[0052] Example 4 A mechanical stirrer and a gas inlet with a thermometer were installed sequentially on a 500 mL three-necked flask. 180 g of diphenyl sulfone, 13.41 g (0.072 mol) of biphenyl hydroquinone, 34.81 g (0.108 mol) of 1,4'-bis(fluorobenzoyl)benzene, 1.79 g of anhydrous potassium carbonate, 12.36 g of anhydrous sodium carbonate, and 72 mL of xylene were added to the reaction flask. A reflux condenser with a water-carrying device was installed on the three-necked flask. The reaction system was polymerized at 170 °C under an argon atmosphere (reflux with water-carrying) for 2 h. The reaction temperature was then raised to 220 °C and polymerized for 1 h, followed by a further increase to 250 °C and another 1 h of polymerization, followed by cooling to 150 °C. 12.10 g (0.036 mol) of hexafluorobisphenol A and 72 mL of diphenyl sulfone were added to the reaction system. Toluene was added, and a reflux condenser with a water-carrying device was installed on a three-necked flask. The reaction system was polymerized at 170°C under an argon atmosphere (reflux with water) for 2 hours. The reaction temperature was then increased to 230°C and polymerized for 1 hour. The temperature was then increased to 260°C and polymerized for 1 hour, during which an increase in viscosity was observed. The temperature was then increased to 290°C and polymerized for 4 hours. The resulting mixture was poured into deionized water under stirring. After cooling to 25°C, the mixture was filtered. The solid obtained from the filtration was pulverized using a high-speed pulverizer and washed 6 times under reflux with acetone. The solid was then filtered again. The solid obtained from the filtration was washed 5 times under reflux with deionized water. The solid obtained from the filtration was then dried in a vacuum oven at 120°C for 24 hours. The resulting solid powder was a fluorinated semi-crystalline polyarylether ketone with the structure shown in Formula V. The obtained solid powder was hot-pressed at 400℃ and 10MPa for 1 hour, and then heat-treated at 300℃ for 4 hours to obtain a polymer film material.

[0053] Example 5 A mechanical stirrer and a gas inlet with a thermometer were installed sequentially on a 500 mL three-necked flask. 180 g of diphenyl sulfone, 10.71 g (0.05 mol) of 4,4'-dihydroxybenzophenone, 32.55 g (0.101 mol) of 1,4'-bis(fluorobenzoyl)benzene, 1.66 g of anhydrous potassium carbonate, 11.45 g of anhydrous sodium carbonate, and 72 mL of xylene were added to the reaction flask. A reflux condenser connected to the flask was installed on the three-necked flask. The reaction system was polymerized at 170 °C under an argon atmosphere (reflux condenser) for 2 h. The reaction temperature was then increased to 220 °C and polymerized for 1 h, followed by increasing the temperature to 250 °C and polymerizing for another 1 h, then cooling to 150 °C. 16.81 g (0.05 mol) of hexafluorobisphenol A and 72 mL of xylene were added to the reaction system. mL of xylene was added, and a reflux condenser with a water-carrying device was installed on a three-necked flask. The reaction system was polymerized at 170°C under an argon atmosphere (reflux with water) for 2 hours. The reaction temperature was then increased to 230°C and polymerized for 1 hour. The temperature was then increased to 250°C and polymerized for 1 hour. An increase in the viscosity of the system was observed. The temperature was then increased to 280°C and polymerized for 4 hours. The resulting mixture was poured into deionized water under stirring. After cooling to 25°C, the mixture was filtered. The solid obtained from the filtration was pulverized using a high-speed pulverizer and washed 6 times under reflux with acetone. The solid was then filtered. The solid obtained from the filtration was washed 5 times under reflux with deionized water. The solid obtained from the filtration was then dried in a vacuum oven at 120°C for 24 hours. The resulting solid powder was a fluorinated semi-crystalline polyarylether ketone with the structure shown in Formula III. The obtained solid powder was hot-pressed at 330℃ and 10MPa for 1 hour, and then heat-treated at 280℃ for 4 hours to obtain a polymer film material.

[0054] Example 6 A mechanical stirrer and a gas inlet with a thermometer were installed sequentially on a 500 mL three-necked flask. 180 g of diphenyl sulfone, 15.00 g (0.07 mol) of 4,4'-dihydroxybenzophenone, 34.18 g (0.106 mol) of 1,4'-bis(fluorobenzoyl)benzene, 1.74 g of anhydrous potassium carbonate, 12.02 g of anhydrous sodium carbonate, and 72 mL of xylene were added to the reaction flask. A reflux condenser connected to the flask was installed on the three-necked flask. The reaction system was polymerized at 170 °C under an argon atmosphere (reflux condenser) for 2 h. The reaction temperature was then increased to 220 °C and polymerized for 1 h, followed by increasing the temperature to 250 °C and polymerizing for another 1 h, then cooling to 150 °C. 11.77 g (0.035 mol) of hexafluorobisphenol A and 72 mL of xylene were added to the reaction system. mL of xylene was added, and a reflux condenser with a water-carrying device was installed on a three-necked flask. The reaction system was polymerized at 170°C under an argon atmosphere (reflux with water) for 2 hours. The reaction temperature was then increased to 230°C and polymerized for 1 hour. The temperature was then increased to 250°C and polymerized for 1 hour. An increase in the viscosity of the system was observed. The temperature was then increased to 280°C and polymerized for 4 hours. The resulting mixture was poured into deionized water under stirring. After cooling to 25°C, the mixture was filtered. The solid obtained from the filtration was pulverized using a high-speed pulverizer and washed 6 times under reflux with acetone. The solid was then filtered. The solid obtained from the filtration was washed 5 times under reflux with deionized water. The solid obtained from the filtration was then dried in a vacuum oven at 120°C for 24 hours. The resulting solid powder was a fluorinated semi-crystalline polyarylether ketone with the structure shown in Formula III. The obtained solid powder was hot-pressed at 330℃ and 10MPa for 1 hour, and then heat-treated at 280℃ for 4 hours to obtain a polymer film material.

[0055] Comparative Example 1 Polyphenylsulfone (PPSU) (Radel® R-5000) purchased from Solvay Group in Belgium was hot-pressed at 380°C and 10 MPa for 1 hour to obtain a polymer film material with the following structural formula: .

[0056] Comparative Example 2 Polyetheretherketone (PEEK) (FD-PEEK-550PF) purchased from Zhongyan Polymer Materials Co., Ltd. was hot-pressed at 380℃ and 10MPa for 1 hour, followed by heat treatment at 200℃ for 2 hours to obtain a polymer film material with the following structural formula: .

[0057] The polymer powders from Examples 1-6 and Comparative Examples 1-2 were mixed with different solvents, and their solubility was tested. The results are shown in Table 1.

[0058] Table 1. Solubility of polymer powders from Examples 1-6 and Comparative Examples 1-2 in different solvents

[0059] Note: In Table 1, + indicates soluble; - indicates insoluble.

[0060] As shown in Table 1, the fluorinated semi-crystalline polyarylether ketone provided by the present invention can only be dissolved in concentrated sulfuric acid with a mass concentration of 98%, and is insoluble in most common organic solvents.

[0061] The fluorinated semi-crystalline polyaryletherketones prepared in Examples 2, 4, and 6 were subjected to infrared detection using an IR Tracer-100 Fourier transform infrared spectrometer, and the infrared absorption spectra were obtained, as shown below. Figure 1 As shown. From Figure 1 The presence of strong stretching vibration absorption peaks for ether bonds, carbonyl groups, and carbon-fluorine bonds indicates that the present invention has successfully introduced fluorine-containing groups into polyaryletherketones.

[0062] Thermogravimetric analysis (TGA) was performed on the fluorinated semi-crystalline polyaryletherketone powders prepared in Examples 2, 4, and 6 to obtain TGA images, as shown below. Figure 2 As shown. The thermal properties of the fluorinated semi-crystalline polyaryletherketone powders prepared in Examples 2, 4, and 6 were tested using a CHIP DSC 100 DSC thermal analyzer according to GB / T 19466.1-2004 (the fluorinated semi-crystalline polyaryletherketone powders prepared in Examples 2, 4, and 6 were annealed at 200℃, 250℃, and 250℃ respectively for 4 hours before testing). The DSC charts are shown below. Figure 3 As shown. By Figure 2 , Figure 3 It can be seen that the 5% thermal weight loss temperature of the three fluorinated semi-crystalline polyaryletherketones is higher than 515℃. The DSC test results show that the glass transition temperatures of the fluorinated semi-crystalline polyaryletherketone powders prepared in Examples 2, 4 and 6 are 165℃, 178℃ and 159℃, respectively, and the melting points are 326℃, 357℃ and 315℃, respectively. This indicates that the fluorinated semi-crystalline polyaryletherketones provided by the present invention have good thermal stability, high heat resistance and operating temperature.

[0063] The fluorinated semi-crystalline polyaryletherketone powders prepared in Examples 2, 4, and 6 were analyzed by XRD using a D8 ADVANCE X-ray diffractometer. The XRD patterns are shown below. Figure 4 As shown. By Figure 4 It is known that the fluorinated semi-crystalline polyarylether ketone provided by the present invention has a high degree of crystallinity, which is 21-34%, wherein the crystallinity of Example 2 is 21%, the crystallinity of Example 4 is 34%, and the crystallinity of Example 6 is 27%.

[0064] The mechanical properties of the polymer film materials prepared in Examples 2, 4, and 6 were tested using an AGS-X 500N universal tensile testing machine according to GB / T1040.1-2018. Their stress-strain curves are shown in [Figure 1]. Figure 5 The mechanical properties obtained are listed in Table 2.

[0065] The specific viscosity of the fluorinated semi-crystalline polyaryletherketone powders prepared in Examples 2, 4, and 6 was tested using an Ubbelohde viscometer, and the results were 0.75 dL / g, 0.68 dL / g, and 0.70 dL / g, respectively.

[0066] The high-temperature mechanical properties of the fluorinated semi-crystalline polyaryletherketone powders prepared in Examples 2, 4, and 6 were tested using a DMA1 type dynamic thermomechanical analyzer. The storage modulus test results and DMA (Dynamic Thermomechanical Analysis) curves are shown below. Figure 6 The energy storage modulus at 120°C obtained in Examples 2, 4, and 6 is listed in Table 2.

[0067] Table 2 Physical and mechanical properties of each sample

[0068] Combine Table 2 and Figure 5 It can be seen that the fluorinated semi-crystalline polyaryletherketone provided by the present invention exhibits excellent mechanical properties, with high tensile strength and large elongation at break, proving that it has high mechanical strength and toughness. The tensile strength of the fluorinated semi-crystalline polyaryletherketone film provided by the present invention is 99~105 MPa, and the elongation at break is 20~58%.

[0069] From Table 2 and Figure 6 It can be seen that the storage modulus of the block-type fluorinated semi-crystalline polyarylether ketones provided by this invention is higher than 2.8 GPa. The block-type fluorinated polyarylether ketones with higher crystallinity have higher storage modulus at all temperatures within the test range, indicating that the polymerization and processing methods of the fluorinated semi-crystalline polyarylether ketones provided by this invention have a significant effect on improving their mechanical properties.

[0070] The friction coefficients of the polymer film materials prepared in Examples 2, 4, 6 and Comparative Examples 1-2 were tested at room temperature (25°C) using the reciprocating ball-disc mode of the UMT tribometer (load 30 N, frequency 1 Hz, displacement 5 mm, ball diameter 6 mm, time 1 h). The obtained friction curves are shown below. Figure 7 As shown, the specific friction coefficient and wear track width are listed in Table 3.

[0071] Table 3. Tribological properties of polymer film materials in Examples 2, 4, 6 and Comparative Examples 1-2

[0072] PPSU molecules contain a biphenyl structure, as does the one in Example 4. The difference is that the tetrahedral sulfone groups in PPSU disrupt the regularity of the molecular chain; therefore, PPSU is an amorphous thermoplastic polymer. (Table 3 and...) Figure 7 The results show that the fluorinated semi-crystalline polyaryletherketone provided by this invention has a significantly lower coefficient of friction and a smaller wear track width than PPSU. This indicates that introducing fluorinated groups into the molecular structure of polyaryletherketone can effectively reduce its coefficient of friction and wear rate. Furthermore, due to the ordered nature of the fluorinated polyaryletherketone molecular chain segments, a crystalline structure can be formed in its aggregated state, significantly improving its self-lubricating properties.

[0073] PEEK in Comparative Example 2 is a widely used polyaryletherketone material. Its molecular structure is similar to the fluorinated semi-crystalline polyaryletherketones in Examples 2, 4, and 6, and it has a regular structure and high crystallinity. Compared to PEEK, the fluorinated semi-crystalline polyaryletherketone provided by this invention has slightly lower crystallinity due to the introduction of fluorinated groups, but its molecular chain rigidity is higher than that of PEEK, resulting in a strength of 105 MPa, which is higher than that of PEEK (98 MPa). The friction coefficient of the fluorinated semi-crystalline polyaryletherketone provided by this invention is close to that of PEEK, but the wear track width is reduced by up to 13% compared to PEEK, demonstrating significant wear resistance.

[0074] The water contact angle and ethylene glycol contact angle of the polymer membrane materials in Examples 1-6 and Comparative Examples 1-2 were measured using a Theta Flex contact angle meter; and the surface energy of the polymer membrane materials was calculated using the OWRK method. The specific results are listed in Table 4.

[0075] Table 4. Surface properties of polymer film materials from Examples 1-6 and Comparative Examples 1-2

[0076] Based on Table 4, a bar chart comparing the surface energy of the polymer film materials in Examples 1-6 and Comparative Examples 1-2 was plotted. Figure 8 As shown.

[0077] Combine Table 4 and Figure 8 It can be seen that the polymer film material prepared from fluorinated semi-crystalline polyaryletherketone provided by this invention exhibits significant advantages in terms of surface properties, with lower surface energy (30.3~36.9 mJ / m²) compared to PPSU and PEEK. 2 Its superior hydrophobicity (92.5°~101°) and excellent anti-wetting properties give it an advantage in applications requiring resistance to various liquid adhesions, penetrations, or contamination. This means that the prepared fluorinated polyaryletherketone materials are anti-fouling, easy to clean, moisture-proof, and impermeable.

[0078] The fluorinated semi-crystalline polyaryletherketone provided by this invention possesses self-lubricating properties, good solvent resistance, and excellent mechanical properties, making it suitable for preparing specialized separation and filtration membranes. Simultaneously, its low surface energy / hydrophobic and oleophobic surface effectively resists membrane fouling (organic contaminants, biofouling, oil stains), extending membrane life and reducing cleaning frequency and maintenance costs.

[0079] In addition, in biomedical and medical device applications, low surface energy / hydrophobicity can significantly reduce excessive adhesion of proteins and cells, reduce foreign body reactions and infection risks, and promote tissue integration; when used as surgical instruments and equipment components, it exhibits excellent resistance to biofouling and body fluid adhesion, good biocompatibility, and is easy to clean and disinfect (reducing the risk of cross-infection).

[0080] The advantages of the fluorinated semi-crystalline polyaryletherketone material provided by this invention lie in its excellent hydrophobic and oleophobic properties and low surface energy, which can be directly translated into excellent anti-bioadhesion, anti-fouling, easy-to-clean, moisture-proof, self-lubricating, and chemical-resistant properties. These properties enable its application in high-end biomedical implants and devices, high-frequency electronic substrates, high-performance separation membranes, precision manufacturing demolding, and demanding industrial anti-sticking applications.

[0081] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A fluorinated semi-crystalline polyarylether ketone, characterized in that, It has the structure shown in Equation I: Formula I; Where X includes , or ; a is any integer from 1 to 3, and n is the degree of aggregation.

2. The fluorinated semi-crystalline polyarylether ketone according to claim 1, characterized in that, The fluorinated semi-crystalline polyarylether ketone has the structure shown in any one of formulas II to VII: 。 3. The fluorinated semi-crystalline polyarylether ketone according to claim 1 or 2, characterized in that, The fluorinated semi-crystalline polyaryletherketone has an Ubbelohde viscosity of 0.32–0.96 dL / g, a glass transition temperature of 159–178 °C, a melting point of 315–357 °C, a crystallinity of 20–35%, and a surface energy of 30.3–36.9 mJ / m². 2 .

4. The method for preparing the fluorinated semi-crystalline polyarylether ketone according to any one of claims 1 to 3, characterized in that, Includes the following steps: 1,4'-bis(fluorobenzoyl)benzene, a high-boiling-point solvent, compound 1, an alkali metal salt-forming agent and a first dehydrating agent are mixed and subjected to a first polymerization reaction to obtain an oligomer; The system after the first polymerization reaction, hexafluorobisphenol A, and the second dehydrating agent are mixed and then subjected to a second polymerization reaction to obtain the fluorinated semi-crystalline polyarylether ketone. Compound 1 is X includes , or .

5. The preparation method according to claim 4, characterized in that, The high-boiling-point solvent includes diphenyl sulfone or sulfolane; The alkali metal salt-forming agent includes anhydrous potassium carbonate and / or anhydrous sodium carbonate; The first and second water-removing agents independently include toluene or xylene.

6. The preparation method according to claim 4 or 5, characterized in that, The molar ratio of 1,4'-bis(fluorobenzoyl)benzene to compound 1 is (10~12.5):(4~8); The mass ratio of the total mass of the 1,4'-bis(fluorobenzoyl)benzene and compound 1 to the mass of the high-boiling solvent is (38~50):180; The molar ratio of the 1,4'-bis(fluorobenzoyl)benzene to the alkali metal salt-forming agent is (1~1.3):(1.1~1.3); The mass ratio of the high-boiling-point solvent to the volume ratio of the first dehydrating agent is 5g:(2~5)mL; The first polymerization reaction is a first gradient heating reaction, which includes the following steps in sequence: The temperature is raised to the first reaction temperature to carry out the first reaction, the temperature is raised to the second reaction temperature to carry out the second reaction, and the temperature is raised to the third reaction temperature to carry out the third reaction. The temperature of the first reaction is 160~180℃, and the reaction time is 1~3h; the temperature of the second reaction is 210~230℃, and the reaction time is 0.8~1.2h; the temperature of the third reaction is 240~260℃, and the reaction time is 0.8~1.2h.

7. The preparation method according to claim 4 or 5, characterized in that, The molar ratio of 1,4'-bis(fluorobenzoyl)benzene to hexafluorobisphenol A is (1~1.3):(0.3~0.5); The volume ratio of the second water-removing agent to the mass ratio of the high-boiling-point solvent is (2~5) mL: 5g; The second polymerization reaction is a second gradient heating reaction, which includes the following steps in sequence: The temperature is increased to the fourth reaction temperature to carry out the fourth reaction, the temperature is increased to the fifth reaction temperature to carry out the fifth reaction, the temperature is increased to the sixth reaction temperature to carry out the sixth reaction, and the temperature is increased to the seventh reaction temperature to carry out the seventh reaction. The temperature of the fourth reaction is 160~180℃, and the time of the fourth reaction is 1.5~2.5h; the temperature of the fifth reaction is 220~240℃, and the time of the fifth reaction is 0.8~1.2h; the temperature of the sixth reaction is 240~260℃, and the time of the sixth reaction is 0.8~1.2h; the temperature of the seventh reaction is 270~290℃, and the time of the seventh reaction is 3~5h.

8. The preparation method according to claim 7, characterized in that, The process after the second polymerization reaction also includes post-processing of the system after the second polymerization reaction. The post-processing includes: solid-liquid separation after solid precipitation, and solid obtained by solid-liquid separation is subjected to solid pulverization, primary washing, secondary washing and drying in sequence.

9. A polymer membrane material, characterized in that, The polymer membrane material is prepared from the fluorinated semi-crystalline polyaryletherketone as described in any one of claims 1 to 3 or the fluorinated semi-crystalline polyaryletherketone prepared by the preparation method described in any one of claims 4 to 8.

10. The application of the fluorinated semi-crystalline polyaryletherketone as described in any one of claims 1 to 3, or the fluorinated semi-crystalline polyaryletherketone prepared by the preparation method described in any one of claims 4 to 8, or the polymer membrane material as described in claim 9, in the preparation of biomedical implants, high-frequency electronic substrates, high-performance separation membranes, precision manufacturing demolding, and harsh industrial anti-sticking.

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