Fluorine-containing polyaryletherketone, preparation method and application thereof, polymer membrane material and application thereof

Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to fluorine-containing polyaryletherketone, a preparation method and application thereof, a polymer film material and application thereof. The invention provides fluorine-containing polyaryletherketone which has a structural formula as shown in a formula I. X comprises a: b = (0-0.67): (0.33-1), and a is not equal to 0; n is the degree of polymerization; the crystallinity of the fluorine-containing polyaryletherketone is 15 to 25 percent. A fluorine-containing group with a low surface energy characteristic is introduced into the polyaryletherketone, so that the polyaryletherketone easily falls off in a friction environment and forms a transfer film, and the friction coefficient of the fluorine-containing polyaryletherketone is effectively reduced; meanwhile, the fluorine-containing polyaryletherketone has structural symmetry of molecular chain segments, so that the problem that the crystallinity is remarkably reduced due to the fact that more fluorine-containing groups are added into the polyaryletherketone can be solved, and the crystallinity and modulus of the fluorine-containing polyaryletherketone are effectively maintained; the fluorine-containing polyaryletherketone provided by the invention has a relatively low friction coefficient and also has good mechanical properties.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and in particular relates to a fluorine-containing polyaryletherketone and a preparation method and application thereof, a polymer film material and application thereof. Background Art

[0002] Polyaryletherketone (PAEK) is a type of aromatic crystalline polymer connected by ether bonds, ketone groups and phenylene groups. It has high heat resistance, good dielectric properties, chemical corrosion resistance, radiation resistance and excellent mechanical properties. It is widely used in aerospace, petroleum industry, machinery, electronics, nuclear energy and national defense and military industries. With the development of modern science and technology, higher requirements are placed on the tribological properties of polyaryletherketone. At present, its intrinsic tribological properties are mainly regulated by introducing fluorine-containing groups through random copolymerization. However, the symmetry of the molecular chain structure of polyaryletherketone after the above modification is mostly destroyed, causing the crystallinity of the material to drop sharply (usually less than 10%), resulting in a significant decrease in modulus and tensile strength, and a decrease in solvent resistance, forming a contradictory situation of "reducing the friction coefficient but decreasing the overall performance". Therefore, it is of great significance to develop fluorinated polyaryletherketones with good mechanical properties, friction properties and solvent resistance. Summary of the Invention

[0003] In view of this, the present invention provides a fluorinated polyaryletherketone and a preparation method and application thereof, a polymer film material and application thereof. The fluorinated polyaryletherketone provided by the present invention has good friction properties, mechanical properties and solvent resistance, which expands its application range.

[0004] In order to solve the above technical problems, the present invention provides a fluorinated polyaryletherketone having the structural formula shown in Formula I:

[0005]

[0006] Among them, X includes

[0007] Wherein, a:b=(0~0.67):(0.33~1), a is not equal to 0;

[0008] n is the degree of polymerization;

[0009] The crystallinity of the fluorine-containing polyaryletherketone is 15-25%.

[0010] Preferably, the fluorinated polyaryletherketone has a structure shown in any one of Formulas II to V:

[0011]

[0012] Preferably, the friction coefficient of the fluorinated polyaryletherketone is 0.39-0.47, and the Ubbelohde viscosity is 0.32-0.96 dL·g-1 , the glass transition temperature is 152~163℃, and the melting point is 241~287℃.

[0013] The present invention also provides a method for preparing the fluorinated polyaryletherketone described in the above technical solution, comprising method 1 and method 2. When a:b is greater than or equal to 1, method 1 is used for preparation, and method 1 comprises the following steps:

[0014] Hexafluorobisphenol A, 4,4'-difluorobenzophenone, a first high boiling point solvent, a first alkali metal salt-forming agent, and a first water-carrying agent are mixed and subjected to a first polymerization reaction to obtain a first oligomer;

[0015] The system after the first polymerization reaction is mixed with compound 1 and a second water-carrying agent, and then a second polymerization reaction is carried out to obtain the fluorinated polyaryletherketone; the compound 1 is HO-X-OH, X includes

[0016] When a:b is less than 1, method 2 is used for preparation, and the method 2 comprises the following steps:

[0017] mixing 4,4'-difluorobenzophenone, compound 1, a second high boiling point solvent, a second alkali metal salt-forming agent, and a third water-carrying agent, and then performing a third polymerization reaction to obtain a second oligomer;

[0018] The system after the third polymerization reaction is mixed with hexafluorobisphenol A and a fourth water-carrying agent, and then a fourth polymerization reaction is carried out to obtain the fluorinated polyaryletherketone.

[0019] Preferably, the first high boiling point solvent and the second high boiling point solvent independently include diphenyl sulfone or sulfolane;

[0020] The first alkali metal salt-forming agent and the second alkali metal salt-forming agent independently include anhydrous potassium carbonate and / or anhydrous sodium carbonate;

[0021] The first water-carrying agent, the second water-carrying agent, the third water-carrying agent and the fourth water-carrying agent independently include toluene or xylene.

[0022] Preferably, in the method 1, the molar ratio of hexafluorobisphenol A to 4,4'-difluorobenzophenone is (0.1-0.5):(1-1.05);

[0023] The mass ratio of the total mass of hexafluorobisphenol A, 4,4'-difluorobenzophenone and compound 1 to the first high boiling point solvent is (1-1.05):(2.5-3.5), preferably 1:3;

[0024] The molar ratio of hexafluorobisphenol A to the first alkali metal salt-forming agent is (0.1-0.9):(1.1-1.3);

[0025] The mass ratio of the first high boiling point solvent to the volume ratio of the first water-carrying agent is 5 g: (2-5) mL;

[0026] The first polymerization reaction is a first gradient temperature increase reaction, which sequentially comprises 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;

[0027] The temperature of the first reaction is 160-170°C, and the time of the first reaction is 1-3 hours; the temperature of the second reaction is 220-240°C, and the time of the second reaction is 0.8-1.2 hours; the temperature of the third reaction is 250-280°C, and the time of the third reaction is 0.8-1.2 hours.

[0028] Preferably, the molar ratio of hexafluorobisphenol A to compound 1 in method 1 is (0.5-0.67):(0.33-0.5);

[0029] The mass ratio of the first high boiling point solvent to the volume ratio of the second water-carrying agent is 5g:(2-4)mL;

[0030] The second polymerization reaction is a second gradient temperature increase reaction, which sequentially comprises 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;

[0031] The temperature of the fourth reaction is 160-180°C, and the time of the fourth reaction is 1.5-2.5 hours; the temperature of the fifth reaction is 220-240°C, and the time of the fifth reaction is 0.8-1.2 hours; the temperature of the sixth reaction is 240-260°C, and the time of the sixth reaction is 0.8-1.2 hours; the temperature of the seventh reaction is 260-280°C, and the time of the seventh reaction is 0.8-1.2 hours;

[0032] After the second polymerization reaction, the system after the second polymerization reaction is subjected to post-treatment, and the post-treatment includes: solid-liquid separation after solid precipitation, solid crushing, primary washing, secondary washing and drying of the obtained solid components in sequence.

[0033] Preferably, in the method 2, the molar ratio of 4,4'-difluorobenzophenone to compound 1 is (1-1.05):(0.5-1);

[0034] The mass ratio of the total mass of hexafluorobisphenol A, 4,4'-difluorobenzophenone and compound 1 to the second high boiling point solvent is (1-1.05):(2.5-3.5);

[0035] The molar ratio of the 4,4'-difluorobenzophenone to the second alkali metal salt-forming agent is (1-1.05):(1.1-1.3);

[0036] The mass ratio of the second high boiling point solvent to the volume ratio of the third water-carrying agent is 5g:(2-5)mL;

[0037] The third polymerization reaction is a third gradient temperature increase reaction, and the third gradient temperature increase reaction sequentially comprises the following steps: heating to an eighth reaction temperature for an eighth reaction, heating to a ninth reaction temperature for a ninth reaction, and heating to a tenth reaction temperature for a tenth reaction;

[0038] The temperature of the eighth reaction is 160-180°C, and the time of the eighth reaction is 1-3 hours; the temperature of the ninth reaction is 240-260°C, and the time of the ninth reaction is 0.8-1.2 hours; the temperature of the tenth reaction is 270-290°C, and the time of the tenth reaction is 0.8-1.2 hours.

[0039] Preferably, in the method 2, the molar ratio of 4,4'-difluorobenzophenone to hexafluorobisphenol A is (1-1.05):(0.5-0.9);

[0040] The mass ratio of the second high boiling point solvent to the volume ratio of the fourth water-carrying agent is 5 g: (2-4) mL;

[0041] The fourth polymerization reaction is a fourth gradient temperature increase reaction, and the fourth gradient temperature increase reaction sequentially comprises the following steps: heating to an eleventh reaction temperature for an eleventh reaction, heating to a twelfth reaction temperature for a twelfth reaction, heating to a thirteenth reaction temperature for a thirteenth reaction, and heating to a fourteenth reaction temperature for a fourteenth reaction;

[0042] The temperature of the eleventh reaction is 160-180°C, and the time of the eleventh reaction is 0.8-1.2 hours; the temperature of the twelfth reaction is 220-240°C, and the time of the twelfth reaction is 0.8-1.2 hours; the temperature of the thirteenth reaction is 240-260°C, and the time of the thirteenth reaction is 0.8-1.2 hours; the temperature of the fourteenth reaction is 260-280°C, and the time of the fourteenth reaction is 3-5 hours;

[0043] After the fourth polymerization reaction, the system after the fourth polymerization reaction is subjected to post-treatment, and the post-treatment includes: solid-liquid separation after solid precipitation, solid crushing, primary washing, secondary washing and drying of the solid obtained by the solid-liquid separation.

[0044] The present invention also provides a polymer film material, which is prepared from the fluorinated polyaryletherketone described in the above technical solution or the fluorinated polyaryletherketone prepared by the preparation method described in the above technical solution.

[0045] The present invention also provides the use of the fluorinated polyaryletherketone described in the above technical solution or the fluorinated polyaryletherketone prepared by the preparation method described in the above technical solution or the polymer film material described in the above technical solution in aerospace, machinery manufacturing or polymer bearings.

[0046] The present invention provides a fluorinated polyaryletherketone having the structural formula shown in Formula I:

[0047]

[0048] Among them, X includes a:b=(0~0.67):(0.33~1), where a is not equal to 0; n is the degree of polymerization; the crystallinity of the fluorinated polyaryletherketone is 15~25%. The present invention introduces fluorinated groups with low surface energy characteristics into the polyaryletherketone, making it easy to form a transfer film in a friction environment, effectively reducing the friction coefficient of the fluorinated polyaryletherketone; at the same time, the fluorinated polyaryletherketone provided by the present invention has structural symmetry and orderliness of the molecular chain segments, which can overcome the problem of significantly reduced crystallinity caused by adding more fluorinated groups to the polyaryletherketone, and effectively maintain its crystallinity and storage modulus; the fluorinated polyaryletherketone provided by the present invention has a low friction coefficient and good mechanical properties and solvent resistance.

[0049] During the preparation process of the present invention, fluorine groups are introduced into the polyaryletherketone by a step-by-step polymerization method, thereby forming a regular and orderly molecular structure. Different structural units are selected for polymerization during the step-by-step polymerization process to adjust the structural symmetry of its molecular chain segments. This can overcome the problem of a significant decrease in crystallinity caused by the addition of more fluorine-containing groups to the polyaryletherketone, and effectively maintain its crystallinity and modulus. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 The infrared absorption spectra of the fluorinated polyaryletherketone powder prepared in Examples 1 to 3 are shown;

[0051] Figure 2 This is the TGA graph of the fluorinated polyaryletherketone powder prepared in Examples 1 to 3;

[0052] Figure 3 The DSC graphs of the fluorinated polyaryletherketone powders prepared in Examples 1 to 3 are shown;

[0053] Figure 4 The XRD spectra of the fluorinated polyaryletherketone powder prepared in Examples 1 to 3 are as follows:

[0054] Figure 5 Comparative curves of tensile strength and elongation at break of the fluorinated polyaryletherketone films prepared in Examples 2 and 3 before and after annealing;

[0055] Figure 6 The storage modulus test results of the polymers of Examples 2 to 3 and Comparative Examples 1 to 2 are shown;

[0056] Figure 7 The friction coefficient comparison curves of the fluorinated polyaryletherketone films prepared in Examples 2-3 and Comparative Examples 2-3 are shown. DETAILED DESCRIPTION

[0057] The present invention provides a fluorinated polyaryletherketone having the structural formula shown in Formula I:

[0058]

[0059] Among them, X includes

[0060] a:b=(0~0.67):(0.33~1), wherein a is not equal to 0; a:b can be (0.0~0.5):(0.5~1), and can be specifically 0.33:0.67 or 0.5:0.5.

[0061] In the present invention, n is the degree of polymerization.

[0062] In the present invention, the crystallinity of the fluorinated polyaryletherketone is 15 to 25%, and may be 20 to 25%.

[0063] As a specific embodiment of the present invention, the fluorinated polyaryletherketone may have a structure shown in any one of Formulas II to V:

[0064]

[0065] As a specific embodiment of the present invention, the friction coefficient of the fluorinated polyaryletherketone can be 0.39 to 0.47, or 0.40 to 0.45; the Ubbelohde viscosity of the fluorinated polyaryletherketone can be 0.32 to 0.96 dL·g -1 , and can also be 0.50~0.83dL·g -1 , and can further be 0.60 to 0.70 dL·g -1 The glass transition temperature of the fluorinated polyaryletherketone (DSC test result) may be 152 to 163°C; the melting point of the fluorinated polyaryletherketone may be 241 to 287°C.

[0066] The present invention also provides a method for preparing the fluorinated polyaryletherketone described in the above technical solution, including method 1 and method 2. When a:b is greater than or equal to 1, method 1 is used for preparation, and when a:b is less than 1, method 2 is used for preparation.

[0067] In the present invention, the method 1 comprises the following steps:

[0068] Hexafluorobisphenol A, 4,4'-difluorobenzophenone, a first high boiling point solvent, a first alkali metal salt-forming agent, and a first water-carrying agent are mixed and subjected to a first polymerization reaction to obtain a first oligomer;

[0069] The system after the first polymerization reaction is mixed with compound 1 and a second water-carrying agent, and then a second polymerization reaction is carried out to obtain the fluorinated polyaryletherketone; the compound 1 is HO-X-OH, X includes

[0070] Unless otherwise specified, the materials and equipment used in the present invention are all commercially available products in the art.

[0071] The present invention mixes hexafluorobisphenol A, 4,4'-difluorobenzophenone, a first high boiling point solvent, a first alkali metal salt-forming agent and a first water-carrying agent, and then performs a first polymerization reaction to obtain a first oligomer.

[0072] As a specific embodiment of the present invention, the first high-boiling-point solvent may include diphenyl sulfone or cyclopentane; the first alkali metal salt-forming agent may include anhydrous potassium carbonate and / or anhydrous sodium carbonate, and may specifically be a mixture of anhydrous potassium carbonate and anhydrous sodium carbonate, anhydrous potassium carbonate or anhydrous sodium carbonate. In the present invention, when the first 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:(8-19), or may be 1:(8.5-9.5). As a specific embodiment of the present invention, the first water-carrying agent may include toluene or xylene.

[0073] As a specific embodiment of the present invention, the molar ratio of hexafluorobisphenol A and 4,4'-difluorobenzophenone can be (0.1-0.5):(1-1.05), or (0.3-0.5):(1-1.02), and can be specifically 0.68:1.36 or 0.5:1; the mass ratio of the total mass of hexafluorobisphenol A, 4,4'-difluorobenzophenone and compound 1 to the first high boiling point solvent can be (1-1.05):(2.5-3.5), and can be specifically 1:3; the molar ratio of hexafluorobisphenol A and the first alkali metal salt-forming agent can be (0.1-0.9):(1.1-1.3), or (0.3-0.5):(1.1-1.2), and can be specifically 0.33:1.2; the mass ratio of the first high boiling point solvent to the volume ratio of the first water-carrying agent can be 5g:(2-5)mL, and can be specifically 5g:2mL.

[0074] As a specific embodiment of the present invention, the first polymerization reaction can be a first gradient temperature increase 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°C, or 170-180°C; the time of the first reaction can be 1-3 hours, or 2-3 hours; the temperature of the second reaction can be 220-240°C, or 230-240°C; the time of the second reaction can be 0.8-1.2 hours, or 1-1.2 hours; the temperature of the third reaction can be 250-280°C, or 250-260°C; the time of the third reaction can be 0.8-1.2 hours, or 1-1.2 hours. In the present invention, the gradient temperature increase method can enable the system to undergo sufficient polymerization reaction at each temperature section, regulate the reaction rate, reduce the occurrence of side reactions, ensure the stability of the entire polymerization reaction, and obtain the target linear polymerization product.

[0075] As a specific embodiment of the present invention, the first polymerization reaction can be carried out under a protective atmosphere, which can include argon or nitrogen. By carrying out the first polymerization reaction in a protective atmosphere, the present invention can avoid the high temperature during the reaction process causing oxygen in the air to oxidize the reactants and cause other side reactions.

[0076] As a specific embodiment of the present invention, after the first polymerization reaction, the method may further include: cooling the system after the first polymerization reaction; the temperature after cooling may be 140-150° C. The present invention may continue to heat the system after cooling to perform the second polymerization reaction.

[0077] After obtaining the first oligomer, the present invention mixes the first polymerization reaction system, compound 1, and a second water-carrying agent, and then conducts a second polymerization reaction to obtain the fluorinated polyaryletherketone.

[0078] As a specific embodiment of the present invention, the second water-carrying agent may include toluene or xylene. As a specific embodiment of the present invention, the molar ratio of hexafluorobisphenol A to compound 1 may be (0.5-0.67):(0.33-0.5), specifically 1:1 or 2:1; the mass ratio of the first high-boiling point solvent to the volume ratio of the second water-carrying agent may be 5g:(2-4)mL, specifically 5g:2mL.

[0079] As a specific embodiment of the present invention, the second polymerization reaction can be a second gradient temperature increase reaction, and the second gradient temperature increase reaction 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°C, specifically 160°C, 165°C, 170°C, 175°C or 180°C; the time of the fourth reaction can be 1.5-2.5h, specifically 1.5h, 2h or 2.5h; the temperature of the fifth reaction can be 2 20~240℃, specifically 220℃, 225℃, 230℃, 235℃ or 240℃; the time of the fifth reaction can be 0.8~1.2h, specifically 1h; the temperature of the sixth reaction can be 240~260℃, specifically 240℃, 245℃, 250℃, 255℃ or 260℃; the time of the sixth reaction can be 0.8~1.2h, specifically 1h; the temperature of the seventh reaction can be 260~280℃, specifically 260℃, 265℃, 270℃, 275℃ or 280℃; the time of the seventh reaction can be 0.8~1.2h, specifically 1h.

[0080] As a specific embodiment of the present invention, the second polymerization reaction can be carried out under a protective atmosphere, which can include argon or nitrogen. By carrying out the second polymerization reaction in a protective atmosphere, the present invention can avoid the high temperature during the reaction process causing oxygen in the air to oxidize the reactants and cause other side reactions.

[0081] Taking the preparation of a fluorinated polyaryletherketone having a ratio of a to b of 1:1 as an example, the equations for the first polymerization reaction and the second polymerization reaction are as follows:

[0082]

[0083] As a specific embodiment of the present invention, the second polymerization reaction may further include post-treatment of the system after the second polymerization reaction, and the post-treatment may include solid-liquid separation after solid precipitation, and solid crushing, primary washing, secondary washing and drying of the solid obtained by the solid-liquid separation.

[0084] As a specific embodiment of the present invention, the solvent for solid precipitation can be water, and the water can be deionized water; the temperature of the solvent can be room temperature, and the temperature of the room temperature can be 20-35°C, or 25-30°C; the specific embodiment of the solid precipitation can be: pouring the polymer mixture into the solvent, and the polymer precipitates.

[0085] As a specific embodiment of the present invention, the system after solid precipitation can be cooled before solid-liquid separation. The temperature after cooling can be room temperature, and the temperature of the room temperature can be 20-30°C. The present invention has no special requirements for the cooling method. The present invention has no special requirements for the specific embodiment of the solid-liquid separation, as long as solid-liquid separation can be achieved. In an embodiment of the present invention, the solid-liquid separation is performed by filtration.

[0086] In the present invention, the solid pulverization can be carried out in a high-speed pulverizer. The present invention has no special requirements on the particle size of the product after the solid pulverization. The present invention can make the subsequent washing more sufficient through pulverization.

[0087] As a specific embodiment of the present invention, the washing solvent for the one-time washing can be acetone, ethanol or ethyl acetate, the washing method can be heating reflux washing, and the number of washing times can be 6 to 8 times, or even 7 to 8 times.

[0088] As a specific embodiment of the present invention, the washing solvent for the secondary washing may be water, the water may be deionized water, the washing method may be heating reflux washing, and the number of washing times may be 5 to 6 times.

[0089] The present invention can perform solid-liquid separation after each washing, and the solid product after solid-liquid separation can be washed again. The present invention has no special requirements for the specific implementation of the solid-liquid separation, as long as solid-liquid separation can be achieved. In an embodiment of the present invention, the solid-liquid separation is performed by filtration.

[0090] The invention removes the high boiling point solvent by one washing step and removes the impurity components including the alkali metal salt by two washing steps.

[0091] The present invention dries the solid product after secondary washing. The drying temperature can be 110-130° C., or 115-120° C.; the drying time can be 22-26 hours, or 24-25 hours; and the drying can be performed in a vacuum oven.

[0092] In the present invention, the method 2 comprises the following steps:

[0093] mixing 4,4'-difluorobenzophenone, compound 1, a second high boiling point solvent, a second alkali metal salt-forming agent, and a third water-carrying agent, and then performing a third polymerization reaction to obtain a second oligomer;

[0094] The system after the third polymerization reaction is mixed with hexafluorobisphenol A and a fourth water-carrying agent, and then a fourth polymerization reaction is carried out to obtain the fluorinated polyaryletherketone.

[0095] In the present invention, 4,4'-difluorobenzophenone, compound 1, a second high boiling point solvent, a second alkali metal salt-forming agent and a third water-carrying agent are mixed and then subjected to a third polymerization reaction to obtain a second oligomer.

[0096] As a specific embodiment of the present invention, the second high boiling point solvent may include diphenyl sulfone or cyclopentane; the second alkali metal salt-forming agent may include anhydrous potassium carbonate and / or anhydrous sodium carbonate, and may specifically be a mixture of anhydrous potassium carbonate and anhydrous sodium carbonate, anhydrous potassium carbonate or anhydrous sodium carbonate. In the present invention, when the second 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:(8-19), or may be 1:(8.5-9.5). As a specific embodiment of the present invention, the third water-carrying agent may include toluene or xylene.

[0097] As a specific embodiment of the present invention, the molar ratio of the 4,4'-difluorobenzophenone and compound 1 can be (1-1.05): (0.5-1), or (1-1.02): (0.5-0.67), and can be specifically 1.5:1; the mass ratio of the total mass and the second high boiling point solvent can be (1-1.05): (2.5-3.5), and can be specifically 1:3; the molar ratio of the 4,4'-difluorobenzophenone and the second alkali metal salt-forming agent can be (1-1.05): (1.1-1.3), or (1-1.02): (1.15-1.2), and can be specifically 1:1.2 or 1:1.18; the mass ratio of the second high boiling point solvent to the volume ratio of the third water-carrying agent is 5g: (2-5) mL, and can be specifically 5g: 2 mL.

[0098] As a specific embodiment of the present invention, the third polymerization reaction is a third gradient temperature increase reaction, and the third gradient temperature increase reaction sequentially comprises the following steps: heating to an eighth reaction temperature for an eighth reaction, heating to a ninth reaction temperature for a ninth reaction, and heating to a tenth reaction temperature for a tenth reaction; the temperature of the eighth reaction may be 160 to 180°C, specifically 160°C, 165°C, 170°C, 175°C or 180°C; the time of the eighth reaction may be 1 to 3 hours, specifically 1 hour , 1.5h, 2h, 2.5h or 3h; the temperature of the ninth reaction may be 240-260°C, specifically 240°C, 245°C, 250°C, 255°C or 260°C; the time of the ninth reaction may be 0.8-1.2h, specifically 1h; the temperature of the tenth reaction may be 270-290°C, specifically 270°C, 275°C, 280°C, 285°C or 290°C; the time of the tenth reaction may be 0.8-1.2h, specifically 1h.

[0099] As a specific embodiment of the present invention, the third polymerization reaction can be carried out under a protective atmosphere, which can include argon or nitrogen. By carrying out the third polymerization reaction in a protective atmosphere, the present invention can avoid the high temperature during the reaction process causing oxygen in the air to oxidize the reactants and cause other side reactions.

[0100] As a specific embodiment of the present invention, after the third polymerization reaction, the process may further include: cooling the system after the third polymerization reaction; the temperature after cooling may be 140-150° C. The present invention may further increase the temperature after cooling to perform the fourth polymerization reaction.

[0101] After obtaining the second oligomer, the present invention mixes the system after the third polymerization reaction with hexafluorobisphenol A and a fourth water-carrying agent and then conducts a fourth polymerization reaction to obtain the fluorinated polyaryletherketone.

[0102] As a specific embodiment of the present invention, the fourth water-carrying agent may include toluene or xylene; the molar ratio of the 4,4'-difluorobenzophenone and hexafluorobisphenol A may be (1-1.05):(0.3-0.5), or (1-1.02):(0.3-0.4), and may be specifically 3:1; the mass ratio of the second high-boiling point solvent to the volume ratio of the fourth water-carrying agent may be 5g:(2-4)mL, and may be specifically 5g:2mL.

[0103] As a specific embodiment of the present invention, the fourth polymerization reaction can be a fourth gradient temperature increase reaction, and the fourth gradient temperature increase reaction can sequentially include the following steps: heating to the eleventh reaction temperature for the eleventh reaction, heating to the twelfth reaction temperature for the twelfth reaction, heating to the thirteenth reaction temperature for the thirteenth reaction, and heating to the fourteenth reaction temperature for the fourteenth reaction. As a specific embodiment of the present invention, the temperature of the eleventh reaction can be 160-180°C, specifically 160°C, 165°C, 170°C, 175°C or 180°C; the time of the eleventh reaction can be 0.8-1.2h, specifically 1h; the temperature of the twelfth reaction can be 220-240°C, specifically 220°C, 225°C, 230°C, 235°C or 240°C; the time of the twelfth reaction can be 0.8-1.2h, specifically 1h. h; the temperature of the thirteenth reaction may be 240-260°C, specifically 240°C, 245°C, 250°C, 255°C or 260°C; the time of the thirteenth reaction may be 0.8-1.2h, specifically 1h; the temperature of the fourteenth reaction may be 260-280°C, specifically 260°C, 265°C, 270°C, 275°C or 280°C; the time of the fourteenth reaction may be 3-5h, specifically 3h, 3.5h, 4h, 4.5h or 5h.

[0104] As a specific embodiment of the present invention, the fourth polymerization reaction can be carried out under a protective atmosphere, which can include argon or nitrogen. By carrying out the fourth polymerization reaction in a protective atmosphere, the present invention can avoid the high temperature during the reaction process causing oxygen in the air to oxidize the reactants and cause other side reactions.

[0105] Taking the preparation of a fluorinated polyaryletherketone having a structure represented by Formula I with a ratio of a:b of 1:2 as an example, the equations for the third polymerization reaction and the fourth polymerization reaction are as follows:

[0106]

[0107] As a specific embodiment of the present invention, the fourth polymerization reaction may further include post-processing the system after the fourth polymerization reaction. The post-processing method may be consistent with the post-processing method after the second polymerization reaction, and will not be repeated here.

[0108] The present invention constructs an ordered microscopic molecular sequence and crystalline structure within the aggregated structure of a fluorinated poly(aryletherketone) through chemical modification and post-treatment. The crystalline fluorinated poly(aryletherketone) provided by the present invention has a low friction coefficient, good processability, and excellent solvent resistance and mechanical properties. The present invention employs a step-by-step nucleophilic substitution copolymerization method. This method has a simple synthesis and molding process, making it suitable for industrial production and ensuring good symmetry of the fluorinated poly(aryletherketone).

[0109] The fluorinated polyaryletherketone powder prepared in the examples can be annealed to prepare a DSC test sample to test its glass transition temperature and melting point. In a specific embodiment of the present invention, the annealing temperature can be 200-250°C, or 220-240°C, for 4-5 hours; the annealing can be performed in a vacuum oven.

[0110] The present invention also provides a polymer film material, which is prepared from the fluorinated polyaryletherketone described in the above technical solution or the fluorinated polyaryletherketone prepared by the preparation method described in the above technical solution.

[0111] In the present invention, the method for preparing a polymer film using fluorinated polyaryletherketone may include the following steps: shaping the fluorinated polyaryletherketone to obtain the polymer film.

[0112] In the present invention, the forming may be hot pressing forming, the temperature of the hot pressing forming may be 310-330° C., or 320-325° C.; the pressure of the hot pressing forming may be 8-12 MPa, or 9-10 MPa.

[0113] As a specific embodiment of the present invention, the molding process may further include annealing the molded product. In the present invention, the annealing temperature may be 210-230°C, or 215-220°C; the annealing time may be 3-5 hours, or specifically 4 hours. In the present invention, the annealing process allows the uncrystallized molecular segments in the aggregated structure of the molded product to continue to align in an orderly manner, forming more complete crystalline regions and thereby improving its crystallinity.

[0114] In the present invention, the polymer film has good mechanical properties and a low friction coefficient and can be used in the fields of aerospace, machinery manufacturing or polymer bearings.

[0115] The present invention also provides the use of the fluorinated polyaryletherketone described in the above technical solution or the fluorinated polyaryletherketone prepared by the preparation method described in the above technical solution or the polymer film material described in the above technical solution in aerospace, machinery manufacturing or polymer bearings.

[0116] In order to further illustrate the present invention, the technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0117] In the following examples, the structural formula of diphenyl sulfone is The structural formula of hexafluorobisphenol A (bisphenol AF) is The structural formula of 4,4'-difluorobenzophenone is The structural formula of hydroquinone is

[0118] Example 1

[0119] A mechanical stirring device and a gas port with a thermometer were installed in sequence on a 500 mL three-necked flask, and 180 g (0.75 mol) of diphenyl sulfone, 22.86 g (0.068 mol) of hexafluorobisphenol A, 29.68 g (0.136 mol) of 4,4'-difluorobenzophenone, 2.26 g (0.0164 mol) of anhydrous potassium carbonate, 15.57 g (0.15 mol) of anhydrous sodium carbonate, and 72 mL of xylene were added to the reaction flask. A water concentrator connected to a reflux condenser was installed on the three-necked flask; the reaction system was polymerized at 170°C (reflux with water) for 2 h under an argon atmosphere, the reaction temperature was raised to 230°C for polymerization for 1 h, the temperature was raised to 250°C for polymerization for 1 h, and then cooled to 150°C; 7.49 g (0.068 mol) of the reaction system was added to the reaction system. ) hydroquinone and 72 mL of xylene, and then install a water concentrator connected to a reflux condenser on a three-necked flask; the reaction system is polymerized at 170° C. under an argon atmosphere (reflux with water) for 2 hours, the reaction temperature is raised to 230° C. for polymerization for 1 hour, and then raised to 250° C. for polymerization for 1 hour. It can be observed that the viscosity of the system increases, and the temperature is raised to 270° C. for polymerization for 4 hours; the reacted system is poured into deionized water kept in a stirring state, cooled to 25° C. and then filtered, the filtered solid is crushed with a high-speed crusher and washed with acetone by heating and reflux for 6 times, and filtered; the filtered solid is heated and refluxed with deionized water and washed 5 times, and filtered; the filtered solid is placed in a vacuum oven at 120° C. and dried for 24 hours to obtain a fluorinated polyaryletherketone powder (b-FPEEK-F50) having the structural formula shown in Formula II.

[0120] The b-FPEEK-F50 powder was hot-pressed at 320°C and 10 MPa and then annealed at 220°C for 4 h to obtain a polymer b-FPEEK-F50 film.

[0121] Example 2

[0122] A mechanical stirring device and a gas port with a thermometer were installed in sequence on a 500 mL three-necked flask, and 180 g of diphenyl sulfone, 10.90 g (0.10 mol) of hydroquinone, 32.40 g (0.15 mol) of 4,4'-difluorobenzophenone, 2.46 g (0.018 mol) of anhydrous potassium carbonate, 17.00 g (0.16 mol) of anhydrous sodium carbonate, and 72 mL of xylene water agent were added to the reaction flask. A water dispenser with a reflux condenser was installed on the three-necked flask; the reaction system was polymerized at 170 ° C. (reflux with water) for 2 h under argon atmosphere, the reaction temperature was raised to 250 ° C. for polymerization for 1 h, then raised to 280 ° C. for polymerization for 1 h, and then cooled to 150 ° C.; 16.64 g (0.05 mol) of bisphenol AF and 72mL of xylene, and then install a water container connected to a reflux condenser on the three-necked flask; the reaction system is polymerized at 170°C under an argon atmosphere (reflux with water) for 2h, the reaction temperature is raised to 230°C, the polymerization reaction is carried out for 1h, the temperature is raised to 250°C, the polymerization reaction is carried out for 1h, it can be observed that the viscosity of the system increases, and the temperature is raised to 270°C for polymerization for 4h; the reaction mixture is poured into deionized water kept in a stirring state, cooled to 25°C and filtered, the filtered solid is crushed with a high-speed crusher and then heated and refluxed with acetone for 6 times, and filtered; the filtered solid is heated and refluxed with deionized water for 5 times, and filtered; the filtered solid is placed in a vacuum oven at 120°C and dried for 24h to obtain a fluorinated polyaryletherketone powder (b-FPEEK-F33) having the structural formula shown in Formula III;

[0123] The b-FPEEK-F33 powder was hot-pressed at 320°C and 10 MPa, and then annealed at 220°C for 4 h to obtain a polymer b-FPEEK-F33 film.

[0124] Example 3

[0125] A mechanical stirring device and a gas port with a thermometer were installed in sequence on a 500 mL three-necked flask, and 180 g of diphenyl sulfone, 20.51 g (0.06 mol) of bisphenol AF, 26.62 g (0.12 mol) of 4,4'-difluorobenzophenone, 2.02 g of anhydrous potassium carbonate, 13.96 g of anhydrous sodium carbonate, and 72 mL of xylene were added to the reaction flask. A water concentrator connected to a reflux condenser was installed on the three-necked flask; the reaction system was polymerized at 170 ° C. (reflux with water) for 2 h under an argon atmosphere, the reaction temperature was raised to 230 ° C. for polymerization for 1 h, then raised to 250 ° C. for polymerization for 1 h, and then cooled to 150 ° C.; 13.07 g (0.06 mol) of 4,4'-dihydroxybenzophenone and 72 mL of xylene were added to the reaction system. , and then install a water container connected to a reflux condenser on the three-necked flask; the reaction system is polymerized at 170°C under an argon atmosphere (reflux with water) for 2 hours, the reaction temperature is raised to 230°C, the polymerization reaction is carried out for 1 hour, the temperature is raised to 250°C, the polymerization reaction is carried out for 1 hour, it can be observed that the viscosity of the system increases, and the temperature is raised to 270°C for polymerization for 4 hours; the reaction mixture is poured into deionized water kept in a stirring state, cooled to 25°C and filtered, the filtered solid is crushed with a high-speed crusher and then washed with acetone for 6 times by heating and reflux, and filtered; the filtered solid is heated and refluxed with deionized water for 5 times and filtered; the filtered solid is placed in a vacuum oven at 120°C and dried for 24 hours to obtain a fluorinated polyaryletherketone powder (b-FPEK-F50) having the structural formula shown in Formula IV;

[0126] The b-FPEK-F50 powder was hot-pressed at 320°C and 10 MPa, and then annealed at 220°C for 4 hours to obtain a polymer b-FPEK-F50 film.

[0127] Comparative Example 1

[0128] The raw materials and proportions are consistent with those in Example 2, except that no step-by-step reaction is performed. All the raw materials are added together when the reaction is fed, that is, a random copolymerization polymerization method is adopted. The specific process is as follows: a mechanical stirring device and a gas port with a thermometer are sequentially installed on a 500 mL three-necked flask, 180 g of diphenyl sulfone, 10.90 g (0.10 mol) of hydroquinone, 32.40 g (0.15 mol) of 4,4'-difluorobenzophenone, 16.64 g (0.05 mol) of bisphenol AF, 2.46 g of anhydrous potassium carbonate, 17.00 g of anhydrous sodium carbonate, and 72 mL of xylene water agent are added to the reaction flask, and a water device connected to a reflux condenser is installed in the reaction flask. 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, the polymerization reaction was carried out for 1 hour, the temperature was raised to 250°C, the polymerization reaction was carried out for 1 hour, it was observed that the viscosity of the system increased, and the temperature was raised to 270°C for polymerization for 4 hours; the reaction mixture was poured into deionized water kept in a stirring state, cooled to 25°C and filtered, the filtered solid was crushed with a high-speed grinder and washed with acetone by heating and reflux for 6 times, and filtered; the filtered solid was washed with deionized water by heating and reflux for 5 times, and filtered; the filtered solid was placed in a vacuum oven at 120°C and dried for 24 hours to obtain a polymer powder recorded as r-FPEEK-F33;

[0129] The r-FPEEK-F33 powder was hot-pressed at 320°C and 10 MPa, and then annealed at 220°C for 4 h to obtain a polymer r-FPEEK-F33 film.

[0130] Comparative Example 2

[0131] The raw materials and proportions are consistent with those in Example 3, except that no step-by-step reaction is carried out. All raw materials are added together when the reaction is fed, that is, a random copolymerization polymerization method is adopted. The specific preparation steps refer to Comparative Example 1. The obtained polymer powder is r-FPEK-F50, and the subsequent processing method consistent with Example 3 is adopted to prepare an r-FPEK-F50 film as a comparative example of Example 3.

[0132] Comparative Example 3

[0133] A polymer film prepared from polysulfone (PSF) with a similar chemical structure was used as a comparative example.

[0134] Test description and results:

[0135] The solubility of Examples 1 to 3 and Comparative Examples 1 to 3 in different solvents was tested. The results are shown in Table 1.

[0136] Table 1 Solubility results of polymers of Examples 1 to 3 and Comparative Examples 1 to 3 in different organic solvents

[0137]

[0138]

[0139] Note: In Table 1, + indicates soluble; - indicates insoluble; +- indicates slightly soluble after heating.

[0140] As shown in Table 1, the fluorinated polyaryletherketone 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.

[0141] The fluorinated polyaryletherketones prepared in Examples 1 to 3 were subjected to infrared detection using an IR Tracer-100 Fourier transform infrared spectrometer to obtain infrared absorption spectra, as shown in FIG. Figure 1 As shown. Figure 1 Strong stretching vibration absorption peaks of ether bonds, carbonyl groups and carbon-fluorine bonds can be seen, indicating that this polymerization method can successfully introduce fluorine-containing groups into the main chain of polyaryletherketone.

[0142] The fluorinated polyaryletherketone powders prepared in Examples 1 to 3 were subjected to thermogravimetric testing to obtain TGA graphs, as shown in FIG. Figure 2 As shown. The thermal properties of the fluorinated poly(aryletherketone) powders prepared in Examples 1 to 3 were tested using a CHIP DSC 100 DSC thermal analyzer in accordance with GB / T 19466.1-2004 (before testing, the fluorinated poly(aryletherketone) powders prepared in Examples 1, 2, and 3 were annealed at 200°C, 250°C, and 250°C for 4 hours, respectively). DSC graphs were obtained, as shown in FIG. Figure 3 As shown. Figure 2 、 Figure 3 It can be seen that the 5% thermal weight loss temperatures of the three fluorinated polyaryletherketones are higher than 515°C. The DSC test results show that the glass transition temperatures of the fluorinated polyaryletherketone powders prepared in Examples 1, 2, and 3 are 156°C, 153°C, and 163°C, respectively, and the melting points are 241°C, 283°C, and 287°C, respectively. This indicates that the fluorinated polyaryletherketone provided by the present invention has good thermal stability, a high heat resistance grade, and a usable temperature. At the same time, since the melting point is lower than that of traditional polyaryletherketones, the processing difficulty and cost are reduced accordingly.

[0143] The fluorinated polyaryletherketone powders prepared in Examples 1 to 3 were subjected to XRD analysis using a D8 ADVANCE X-ray diffractometer, and the XRD patterns were as follows: Figure 4 As shown. Figure 4 It can be seen that the fluorinated polyaryletherketone provided by the present invention has a relatively high crystallinity of 15-25%, wherein the crystallinity of Example 1 is 15%, the crystallinity of Example 2 is 19%, and the crystallinity of Example 3 is 25%.

[0144] The mechanical properties of the films before and after annealing after hot pressing of Examples 1 to 3 were tested using an AGS-X 500N universal tensile testing machine in accordance with GB / T1040.1-2018. The results are shown in Table 1. Figure 5 , the specific values ​​are listed in Table 2.

[0145] The viscosities of the fluorinated poly(aryletherketone) powders prepared in Examples 1, 2, and 3 were measured using an Ubbelohde viscometer and were found to be 0.66 g / dL, 0.64 g / dL, and 0.65 g / dL, respectively.

[0146] Table 2 Physical parameters and mechanical properties of each sample

[0147]

[0148] Combined with Table 2 and Figure 5 It can be seen that the fluorinated polyaryletherketone provided by the present invention shows excellent mechanical properties. The tensile strength of the fluorinated polyaryletherketone film provided by the present invention is 75.5-94.2MPa (75.5-83.2MPa before annealing) (91.1-94.2MPa after annealing), and the elongation at break is 10-185% (91-185% before annealing) (10-93% after annealing). The fluorinated polyaryletherketone film provided by the present invention has both high tensile strength and large elongation at break, which proves that the fluorinated polyaryletherketone provided by the present invention has excellent toughness. At the same time, the tensile strength of the annealed sample is significantly higher than that of the untreated sample, which also proves that the mechanical strength of the fluorinated polyaryletherketone can be improved by annealing. This is because after annealing, the crystallinity of the fluorinated polyaryletherketone increases during the annealing process, resulting in improved mechanical properties, and the improvement effect is very obvious.

[0149] The high temperature mechanical properties of the polymers of Examples 1 to 3 and Comparative Examples 1 to 3 were tested using a DMA1 dynamic thermal mechanical analyzer. The storage modulus test results of Examples 2 to 3 and Comparative Examples 1 to 2 are shown in FIG. Figure 6 The storage moduli at 120°C of Examples 1 to 3 and Comparative Examples 1 to 3 are listed in Table 2. Figure 6 It can be seen that the storage modulus of the block fluorinated polyaryletherketone provided by the present invention is 2.5 to 2.7 GPa. Comparison of two random fluorinated polyaryletherketone films prepared by random copolymerization shows that they have higher storage moduli at all temperatures within the test range (110 to 300°C), indicating that the polymerization and processing methods of the block fluorinated polyaryletherketone provided by the present invention have a significant effect on improving its mechanical properties.

[0150] The friction coefficients of Example 3, Comparative Example 2 and Comparative Example 3 at room temperature (25°C) were tested using a reciprocating ball-disc mode of a UMT friction and wear tester (load 30N, frequency 1HZ, displacement 5mm, ball diameter 6mm). Figure 7 The specific results are listed in Table 3.

[0151] Table 3 Friction coefficient

[0152] sample Friction coefficient (1000s) Friction coefficient (3000s) Example 1 0.46 0.46 Example 2 0.44 0.46 Example 3 0.45 0.46 Comparative Example 2 0.51 0.55 Comparative Example 3 0.66 0.72

[0153] Combined with Table 3 and Figure 7 It can be seen that the molecular structure of PSF is similar to that of Example 3 of the present invention, except that the sulfone group of the tetrahedral structure in PSF destroys the regularity of the molecular chain, so PSF is an amorphous thermoplastic polymer. The friction coefficient of the segmented fluorinated polyaryletherketone of Example 2 and Example 3 is significantly lower than that of PSF and random copolymerized polyaryletherketone, which shows that the introduction of fluorinated groups into the molecular structure of polyaryletherketone according to the method provided by the present invention can effectively reduce its friction coefficient. At the same time, due to the orderliness of the segmented polyaryletherketone molecular segments, a crystal structure can be formed in its aggregated structure, so its solvent resistance is also significantly improved compared with PSF.

[0154] Although the above embodiment provides a detailed description of the present invention, it is only a part of the embodiments of the present invention, not all of the embodiments. People can also obtain other embodiments based on this embodiment without creativity, and these embodiments all fall within the scope of protection of the present invention.

Claims

1. A fluorinated polyaryletherketone, characterized in that It has the structural formula shown in Formula I: Among them, X includes Wherein, a:b=(0~0.67):(0.33~1), a is not equal to 0; n is the degree of polymerization; The crystallinity of the fluorine-containing polyaryletherketone is 15-25%.

2. The fluorinated polyaryletherketone according to claim 1, characterized in that The fluorinated polyaryletherketone has a structure shown in any one of Formulas II to V: The friction coefficient of the fluorinated polyaryletherketone is 0.39 to 0.47, and the Ubbelohde viscosity is 0.32 to 0.96 dL·g -1 , the glass transition temperature is 152~163℃, and the melting point is 241~287℃.

3. The method for preparing the fluorinated polyaryletherketone according to claim 1 or 2, characterized in that: The method includes method 1 and method 2. When a:b is greater than or equal to 1, method 1 is used for preparation. The method 1 includes the following steps: Hexafluorobisphenol A, 4,4'-difluorobenzophenone, a first high boiling point solvent, a first alkali metal salt-forming agent, and a first water-carrying agent are mixed and subjected to a first polymerization reaction to obtain a first oligomer; The system after the first polymerization reaction is mixed with compound 1 and a second water-carrying agent, and then a second polymerization reaction is carried out to obtain the fluorinated polyaryletherketone; the compound 1 is HO-X-OH, X includes When a:b is less than 1, method 2 is used for preparation, and the method 2 comprises the following steps: mixing 4,4'-difluorobenzophenone, compound 1, a second high boiling point solvent, a second alkali metal salt-forming agent, and a third water-carrying agent, and then performing a third polymerization reaction to obtain a second oligomer; The system after the third polymerization reaction is mixed with hexafluorobisphenol A and a fourth water-carrying agent, and then a fourth polymerization reaction is carried out to obtain the fluorinated polyaryletherketone.

4. The preparation method according to claim 3, characterized in that The first high boiling point solvent and the second high boiling point solvent independently include diphenyl sulfone or sulfolane; The first alkali metal salt-forming agent and the second alkali metal salt-forming agent independently include anhydrous potassium carbonate and / or anhydrous sodium carbonate; The first water-carrying agent, the second water-carrying agent, the third water-carrying agent and the fourth water-carrying agent independently include toluene or xylene.

5. The preparation method according to claim 3 or 4, characterized in that: In the method 1, the molar ratio of hexafluorobisphenol A to 4,4'-difluorobenzophenone is (0.1-0.5):(1-1.05); The mass ratio of the total mass of hexafluorobisphenol A, 4,4'-difluorobenzophenone and compound 1 to the first high boiling point solvent is (1-1.05):(2.5-3.5), preferably 1:3; The molar ratio of hexafluorobisphenol A to the first alkali metal salt-forming agent is (0.1-0.9):(1.1-1.3); The mass ratio of the first high boiling point solvent to the volume ratio of the first water-carrying agent is 5 g: (2-5) mL; The first polymerization reaction is a first gradient temperature increase reaction, which sequentially comprises the following steps: Raising the temperature to a first reaction temperature for a first reaction, raising the temperature to a second reaction temperature for a second reaction, and raising the temperature to a third reaction temperature for a third reaction; The temperature of the first reaction is 160-170°C, and the time of the first reaction is 1-3 hours; the temperature of the second reaction is 220-240°C, and the time of the second reaction is 0.8-1.2 hours; the temperature of the third reaction is 250-280°C, and the time of the third reaction is 0.8-1.2 hours.

6. The preparation method according to claim 3 or 4, characterized in that: In the method 1, the molar ratio of hexafluorobisphenol A to compound 1 is (0.5-0.67):(0.33-0.5); The mass ratio of the first high boiling point solvent to the volume ratio of the second water-carrying agent is 5g:(2-4)mL; The second polymerization reaction is a second gradient temperature increase reaction, which sequentially comprises the following steps: Raising the temperature to a fourth reaction temperature for a fourth reaction, raising the temperature to a fifth reaction temperature for a fifth reaction, raising the temperature to a sixth reaction temperature for a sixth reaction, and raising the temperature to a seventh reaction temperature for a seventh reaction; The temperature of the fourth reaction is 160-180°C, and the time of the fourth reaction is 1.5-2.5 hours; the temperature of the fifth reaction is 220-240°C, and the time of the fifth reaction is 0.8-1.2 hours; the temperature of the sixth reaction is 240-260°C, and the time of the sixth reaction is 0.8-1.2 hours; the temperature of the seventh reaction is 260-280°C, and the time of the seventh reaction is 0.8-1.2 hours; After the second polymerization reaction, the system after the second polymerization reaction is subjected to post-treatment, and the post-treatment includes: solid-liquid separation after solid precipitation, solid crushing, primary washing, secondary washing and drying of the obtained solid components in sequence.

7. The preparation method according to claim 3 or 4, characterized in that: In the method 2, the molar ratio of 4,4'-difluorobenzophenone to compound 1 is (1-1.05):(0.5-1); The mass ratio of the total mass of hexafluorobisphenol A, 4,4'-difluorobenzophenone and compound 1 to the second high boiling point solvent is (1-1.05):(2.5-3.5); The molar ratio of the 4,4'-difluorobenzophenone to the second alkali metal salt-forming agent is (1-1.05):(1.1-1.3); The mass ratio of the second high boiling point solvent to the volume ratio of the third water-carrying agent is 5g:(2-5)mL; The third polymerization reaction is a third gradient temperature increase reaction, and the third gradient temperature increase reaction sequentially comprises the following steps: Raising the temperature to an eighth reaction temperature to carry out an eighth reaction, raising the temperature to a ninth reaction temperature to carry out a ninth reaction, and raising the temperature to a tenth reaction temperature to carry out a tenth reaction; The temperature of the eighth reaction is 160-180°C, and the time of the eighth reaction is 1-3 hours; the temperature of the ninth reaction is 240-260°C, and the time of the ninth reaction is 0.8-1.2 hours; the temperature of the tenth reaction is 270-290°C, and the time of the tenth reaction is 0.8-1.2 hours.

8. The preparation method according to claim 3 or 4, characterized in that In the method 2, the molar ratio of 4,4'-difluorobenzophenone to hexafluorobisphenol A is (1-1.05):(0.5-0.9); The mass ratio of the second high boiling point solvent to the volume ratio of the fourth water-carrying agent is 5 g: (2-4) mL; The fourth polymerization reaction is a fourth gradient temperature increase reaction, and the fourth gradient temperature increase reaction sequentially comprises the following steps: Raising the temperature to the eleventh reaction temperature for the eleventh reaction, raising the temperature to the twelfth reaction temperature for the twelfth reaction, raising the temperature to the thirteenth reaction temperature for the thirteenth reaction, and raising the temperature to the fourteenth reaction temperature for the fourteenth reaction; The temperature of the eleventh reaction is 160-180°C, and the time of the eleventh reaction is 0.8-1.2 hours; the temperature of the twelfth reaction is 220-240°C, and the time of the twelfth reaction is 0.8-1.2 hours; the temperature of the thirteenth reaction is 240-260°C, and the time of the thirteenth reaction is 0.8-1.2 hours; the temperature of the fourteenth reaction is 260-280°C, and the time of the fourteenth reaction is 3-5 hours; After the fourth polymerization reaction, the system after the fourth polymerization reaction is subjected to post-treatment, and the post-treatment includes: solid-liquid separation after solid precipitation, solid crushing, primary washing, secondary washing and drying of the solid obtained by the solid-liquid separation.

9. A polymer film material, characterized in that The polymer membrane material is prepared from the fluorinated polyaryletherketone according to claim 1 or 2 or the fluorinated polyaryletherketone prepared by the preparation method according to any one of claims 3 to 8.

10. Use of the fluorinated polyaryletherketone according to claim 1 or 2, or the fluorinated polyaryletherketone prepared by the preparation method according to any one of claims 3 to 8, or the polymer film material according to claim 9 in aerospace, machinery manufacturing or polymer bearings.

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