Process for the preparation of polyaryletherketone 3d printing materials containing thermoreversible covalent bonds

Abstract

The application relates to a preparation method of polyaryletherketone 3D printing material containing a thermal reversible covalent bond, which comprises the following steps: 1, obtaining a polyaryletherketone hyperbranched polymer with furan end groups; 2, uniformly mixing three kinds of component substances, the first component substance is the polyaryletherketone hyperbranched polymer with furan end groups obtained in the step 1, the second component substance is a substance containing a maleimide end group, and the third component is a polyaryletherketone; 3, heating, melting and blending the three kinds of uniformly mixed substances to obtain a hyperbranched polymer modified polyaryletherketone 3D printing material containing a thermal reversible covalent bond. The polyaryletherketone hyperbranched polymer is innovatively combined with the thermal reversible covalent bond, the active end groups capable of Diels-Alder reaction are modified and introduced by utilizing the rich and changeable end group functions of the hyperbranched polymer, and the thermal reversible covalent crosslinking network is utilized to improve the interlayer bonding performance of a 3D printing part of the polyaryletherketone material without damaging the processability of the polyaryletherketone material.

Description

Technical Field

[0001] This invention relates to 3D printing polymer material preparation technology, and more specifically, to a method for preparing polyaryletherketone 3D printing materials containing thermally reversible covalent bonds. Background Technology

[0002] Polyaryletherketone (PLEK) plastics are linear thermoplastic polymers whose aromatic groups are linked by ether and ketone bonds. The main chain contains a large number of aromatic groups and polar ketone groups, giving the molecular chain high rigidity and strong intermolecular forces. Simultaneously, the presence of ether bonds also imparts a certain degree of toughness. Therefore, PLEK is a polymer that combines strength and toughness, exhibiting excellent mechanical properties. Furthermore, PLEK also possesses high heat resistance, creep resistance, wear reduction, and corrosion resistance, making it a high-performance engineering plastic with excellent overall properties. In recent years, PLEK materials have been widely used as 3D printing materials to manufacture 3D printed parts with good heat resistance and excellent mechanical properties. However, because 3D printing technology mostly employs a layer-by-layer manufacturing method, the sequential molding of layers often leads to insufficient diffusion of polymer molecules, resulting in weak interlayer adhesion, poor bonding performance, and a tendency for delamination. This causes significant anisotropy in the mechanical properties of 3D printed parts in different directions, hindering the practical application of 3D printed components. To address this issue, this invention employs a hyperbranched polymer of polyaryletherketone (PAEK) with thermally reversible covalent bonds to modify PAEK materials, thereby improving the interlayer bonding performance of 3D printed parts. Hyperbranched PAEK not only possesses the high mechanical strength and good thermal stability of linear PAEK, but also exhibits the properties of hyperbranched polymers, such as low melt viscosity, good solubility, no chain entanglement, and amorphous properties, making it suitable as a viscosity modifier for linear PAEK materials. This invention innovatively introduces furan end groups and maleimide groups into the PAEK hyperbranched polymer system, enabling it to undergo a Diels-Alder reaction at lower temperatures to generate a covalently cross-linked network. This allows cross-linked covalent bonds to form between layers during the 3D printing cooling process, further enhancing interlayer bonding performance. Meanwhile, at the melt processing temperature, the reversible covalent bonds can be broken, and the presence of cross-linked networks will not reduce the processing performance and 3D printing performance of polyaryletherketone materials. In addition, the addition of hyperbranched polymers can also reduce the melt viscosity of polyaryletherketone, enhance the molecular diffusion rate between layers during 3D printing, and further enhance the interlayer bonding performance.

[0003] It should be noted that the information disclosed in the background section above is only used to enhance the understanding of the background of this disclosure, and therefore may include information that does not constitute prior art known to those skilled in the art. Summary of the Invention

[0004] The purpose of this invention is to provide a method for improving the interlayer bonding performance of 3D printed polyaryletherketone materials by modifying the end groups of a hyperbranched polyaryletherketone polymer and utilizing the thermal reversibility of the Diels-Alder reaction.

[0005] The technical solution of this invention is:

[0006] A method for preparing a hyperbranched polymer-modified polyaryletherketone 3D printing material containing thermally reversible covalent bonds is provided, comprising the following steps:

[0007] Step 1: Obtaining hyperbranched polyaryletherketone polymers with furan end groups

[0008] Hydroxyl-terminated polyaryletherketone hyperbranched polymer, furanoyl chloride, and anhydrous aluminum trichloride were added to dichloromethane solvent at a molar ratio of 1:30-60:8-12, and ultrasonically mixed and dissolved. Then, under an inert atmosphere, the reaction was kept at 50℃-80℃ for 4-8 hours to obtain furan-terminated polyaryletherketone hyperbranched polymer.

[0009] In the hydroxyl-terminated polyaryletherketone hyperbranched polymer, the linear unit backbone contains aromatic groups, ether bonds, and ketone bonds, and there is at least one ether bond or ketone bond between adjacent aromatic groups.

[0010] Step 2: Mix the three components evenly. The first component is the polyaryletherketone hyperbranched polymer with furan end groups obtained in Step 1. The second component is a substance containing maleimide end groups. The third component is polyaryletherketone.

[0011] Step 3: Heat, melt, and blend the three uniformly mixed substances to obtain a hyperbranched polymer-modified polyaryletherketone 3D printing material containing thermally reversible covalent bonds.

[0012] Furthermore, the hydroxyl-terminated polyaryletherketone hyperbranched polymer is obtained by the following steps: adding the fluorine-terminated polyaryletherketone hyperbranched polymer, hydroquinone, anhydrous potassium carbonate, and anhydrous sodium carbonate to an N-methylpyrrolidone solvent in a molar ratio of 1:50-80:3-6:6-12, ultrasonically mixing and dissolving, and then reacting fully for 8-12 hours at a reaction temperature of 200℃-230℃ to obtain the hydroxyl-terminated polyaryletherketone hyperbranched polymer.

[0013] A method for preparing a hyperbranched polymer-modified polyaryletherketone 3D printing material containing thermally reversible covalent bonds is provided, comprising the following steps:

[0014] Step 1: Obtaining hyperbranched polyaryletherketone polymers with furan end groups

[0015] Alkoxy-terminated polyaryletherketone hyperbranched polymer, furanoyl chloride, and anhydrous aluminum trichloride were added to dichloromethane solvent at a molar ratio of 1:30-60:8-12, and ultrasonically mixed and dissolved. Then, under an inert atmosphere, the reaction was carried out at 50℃-80℃ for 4-8 hours to obtain furan-terminated polyaryletherketone hyperbranched polymer.

[0016] In the alkoxy-terminated polyaryletherketone hyperbranched polymer, the linear unit backbone contains aromatic groups, ether bonds, and ketone bonds, and there is at least one ether bond or ketone bond between adjacent aromatic groups.

[0017] Step 2: Mix the three components evenly. The first component is the polyaryletherketone hyperbranched polymer with furan end groups obtained in Step 1. The second component is a substance containing maleimide end groups. The third component is polyaryletherketone.

[0018] Step 3: Heat, melt, and blend the three uniformly mixed substances to obtain a hyperbranched polymer-modified polyaryletherketone 3D printing material containing thermally reversible covalent bonds.

[0019] Furthermore, the alkoxy-terminated polyaryletherketone hyperbranched polymer is obtained by the following steps: adding the fluorine-terminated polyaryletherketone hyperbranched polymer, the alkoxy nucleophile, and anhydrous potassium carbonate in a molar ratio of 1:50-80:4-8 to N-methylpyrrolidone solvent, ultrasonically mixing and dissolving, and then reacting fully for 4-8 hours at a reaction temperature of 180℃-200℃ to obtain the alkoxy-terminated polyaryletherketone hyperbranched polymer.

[0020] In another aspect of this disclosure, a method for preparing a hyperbranched polymer-modified polyaryletherketone 3D printing material containing thermally reversible covalent bonds includes the following steps:

[0021] Step 1: Obtaining hyperbranched polyaryletherketone polymers with furan end groups

[0022] The amino-terminated polyaryletherketone hyperbranched polymer, furanoyl chloride, 4-dimethylaminopyridine (DMAP) and triethylamine were added to dichloromethane solvent at a molar ratio of 1:30-60:1-3:20-30 and mixed and dissolved. The mixture was then stirred for at least 24 hours to obtain the furan-terminated polyaryletherketone hyperbranched polymer.

[0023] In the amino-terminated polyaryletherketone hyperbranched polymer, the linear unit backbone contains aromatic groups, ether bonds, and ketone bonds, and there is at least one ether bond or ketone bond between adjacent aromatic groups.

[0024] Step 2: Mix the three components evenly. The first component is the polyaryletherketone hyperbranched polymer with furan end groups obtained in Step 1. The second component is a substance containing maleimide end groups. The third component is polyaryletherketone.

[0025] Step 3: Heat, melt, and blend the three uniformly mixed substances to obtain a hyperbranched polymer-modified polyaryletherketone 3D printing material containing thermally reversible covalent bonds.

[0026] In one exemplary embodiment of this disclosure, the second component is further defined as bismaleimide, wherein the bismaleimide has a melting point between 50 and 320°C and a boiling point above 400°C. More specifically, the bismaleimide is N,N'-(4,4'-methylenediphenyl)bismaleimide, N,N-m-phenylenebismaleimide, or N,N'-tetramethylenebismaleimide. Even further, the molar ratio of the first component, the second component, and the third component in step 2 is 1:20 to 60:5 to 1000.

[0027] Furthermore, the second component is a maleimide-terminated polyaryletherketone hyperbranched polymer. The linear unit backbone of the maleimide-terminated polyaryletherketone hyperbranched polymer includes aromatic groups, ether bonds, and ketone bonds, and there is at least one ether bond or ketone bond between adjacent aromatic groups. (The linear unit backbone of both the furan-terminated and maleimide-terminated hyperbranched polymers is polyaryletherketone, which is to improve compatibility with the matrix polyaryletherketone material after blending.) Even further, in step 2, the molar ratio of the first component, the second component, and the third component is 1:0.5–1.5:5–1000. Furthermore, the maleimide-terminated polyaryletherketone hyperbranched polymer is obtained by the following method: The hydroxyl-terminated polyaryletherketone hyperbranched polymer, maleimide hexanoyl chloride, and anhydrous aluminum trichloride are added to dimethyl sulfoxide solvent at a molar ratio of 1:30–60:8–12 and dissolved. Then, under an inert atmosphere, the reaction is carried out at 50°C–80°C for 8–12 hours to obtain the maleimide-terminated polyaryletherketone hyperbranched polymer. Further, in the maleimide-terminated polyaryletherketone hyperbranched polymer, the linear unit backbone is polyetherketone, polyetheretherketone, or polyetherketoneketone.

[0028] Furthermore, in the furan-terminated polyaryletherketone hyperbranched polymer, the linear unit backbone is polyetherketone, polyetheretherketone, or polyetherketoneketone, with the following structural formulas:

[0029]

[0030]

[0031] Furthermore, in step 1 above, the obtained furan-terminated polyaryletherketone hyperbranched polymer is subjected to precipitation, filtration, washing, and drying.

[0032] Furthermore, the temperature range for heating, melting, and blending in step 3 is 320℃~400℃.

[0033] Furthermore, the third component is one or more of polyetherketone, polyetheretherketone, polyetherketoneketone, and polyetheretherketoneketone.

[0034] Furthermore, the 3D printing material of the present invention is suitable for fused deposition modeling (FDM) 3D printing, selective laser sintering (SLS) 3D printing, and layered solid fabrication 3D printing.

[0035] The technical principle of this invention is as follows:

[0036] The end groups of hyperbranched polymers can be obtained through chemical reactions to form functional groups with furan end groups. The reaction processes for fluorine (—F), hydroxyl (—OH), alkoxy (—OR), and amino (—NH2) are as follows:

[0037]

[0038]

[0039] Hyperbranched polyaryletherketone polymers with furan end groups can undergo a Diels-Alder reaction with substances containing maleimide end groups to form thermally reversible covalent bonds.

[0040]

[0041] The maleimide-terminated polyaryletherketone hyperbranched polymer is obtained by reacting maleimide-based hexanoyl chloride (a compound with a maleimide functional group at one end and an active group at the other end that can chemically react with the end group of the polyaryletherketone hyperbranched polymer) with a hydroxyl-terminated polyaryletherketone hyperbranched polymer. The reaction principle is as follows:

[0042]

[0043] The use of maleimide-based hexanoic acid chloride is not the only option; other methods can be used as alternatives. In practice, a maleimide functional group and an active group that can chemically react with the end groups of the polyaryletherketone hyperbranched polymer are required. Any product possessing the aforementioned functional group and active group can be selectively applied.

[0044] The hyperbranched polymer-modified polyaryletherketone material containing thermally reversible covalent bonds undergoes a reverse Diels-Alder reaction at temperatures exceeding 120°C, resulting in the breakage of covalent bonds and ensuring that the material's processing performance remains unaffected. When the temperature decreases to the range of 80°C to 20°C, the Diels-Alder reaction recurs, forming a covalent cross-linked network and improving the material's mechanical properties.

[0045] The hyperbranched polymer-modified polyaryletherketone material containing thermally reversible covalent bonds is applied to fused deposition modeling, selective laser sintering, and layered solid manufacturing technologies in 3D printing to improve the interlayer bonding performance of 3D printed parts.

[0046] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and are not intended to limit this disclosure.

[0047] The advantages of this invention are: This invention innovatively combines hyperbranched polyaryletherketone (PAEK) polymers with thermally reversible covalent bonds. Utilizing the rich and varied end-group functional groups of the hyperbranched polymer, active end groups capable of undergoing Diels-Alder reactions are introduced through modification. The thermally reversible covalent crosslinking network improves the interlayer bonding performance of 3D printed parts without compromising the processing performance of the PAEK material. This method is pioneering. The end-group modification reactions are diverse and efficient, the reversible reactions can occur repeatedly, and the material can be repeatedly processed and used. The PAEK material modified with hyperbranched polymers containing thermally reversible covalent bonds is prepared using a melt blending method. The preparation method is simple and efficient, suitable for large-scale industrial production. The obtained PAEK material can be applied to various 3D printing manufacturing methods, with a wide range of applications. This is of great significance for breaking through the bottleneck of high-performance polymer additive manufacturing materials and promoting the development of polymer 3D printing applications. Attached Figure Description

[0048] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with this disclosure and, together with the description, serve to explain the principles of this disclosure. It is obvious that the drawings described below are merely some embodiments of this disclosure, and those skilled in the art can obtain other drawings based on these drawings without any inventive effort.

[0049] Figure 1 The image shows the fracture morphology of the tensile mechanical properties of the 3D printing material of this invention as an electron microscope image.

[0050] Figure 2 Electron micrographs of the fracture morphology of tensile mechanical properties of 3D printed materials in the prior art. Detailed Implementation

[0051] The disclosed examples will be described more fully with reference to the accompanying drawings, in which some (but not all) of the disclosed examples are shown. In fact, many different examples may be described, and these examples should not be construed as limited to those set forth herein. Rather, these examples are described so that this disclosure will be thorough and complete, and will fully convey the scope of this disclosure to those skilled in the art.

[0052] Example 1: 60 g (4 mmol) of hydroxyl-terminated polyetheretherketone hyperbranched polymer, 26.1 g (200 mmol) of furanoyl chloride, 5.3 g (40 mmol) of anhydrous aluminum trichloride, and 600 mL of dichloromethane solvent were weighed and added to a 1000 mL three-necked flask. The mixture was ultrasonically mixed and dissolved, and reacted at 60 °C for 8 hours under N2 protection. After the reaction was completed and cooled, the mixture was added to deionized water to precipitate, filtered, washed successively with deionized water and ethanol, and dried to obtain furan-terminated polyetheretherketone hyperbranched polymer. 100 g (6.3 mmol) of a hyperbranched polyetheretherketone (PEEK) polymer with furan end groups, 90.3 g (252 mmol) of N,N'-(4,4'-methylenediphenyl)bismaleimide, and 4000 g (105 mmol) of PEEK material were thoroughly mixed by mechanical stirring. The mixture was then added to a twin-screw extruder and heated for melt blending. The feeding section temperature was 350 °C, the melting section temperature was 370 °C, and the discharge section temperature was 350 °C, resulting in a thermally reversible covalently bonded hyperbranched polymer-modified PEEK material. The modified PEEK material was then powdered and applied to selective laser sintering (SLS) 3D printing.

[0053] Example 2: 50 g (4.2 mmol) of fluorine-terminated polyetherketone hyperbranched polymer, 20.0 g of sodium ethoxide (294 mmol), and 29 g (21 mmol) of anhydrous potassium carbonate were weighed and added to 500 mL of N-methylpyrrolidone solvent. The mixture was ultrasonically mixed and dissolved, and then heated to 200 °C for 6 hours under N2 protection. The reaction mixture was added to deionized water to precipitate, filtered, washed successively with deionized water and ethanol, and dried to obtain ethoxylated polyetherketone hyperbranched polymer. 50 g (4.15 mmol) of ethoxylated polyetherketone hyperbranched polymer, 24.4 g (186.75 mmol) of furanoyl chloride, and 6.64 g (49.8 mmol) of anhydrous aluminum trichloride were added to 500 mL of dichloromethane solvent. The mixture was ultrasonically mixed and dissolved, and then reacted to 70 °C for 8 hours under N2 protection. The reaction mixture was precipitated, filtered, washed, and dried to obtain furan-terminated polyetherketone hyperbranched polymer. 100 g (6.6 mmol) of a hyperbranched polyetherketone polymer with furan end groups, 70.8 g (264 mmol) of N,N-m-phenylenebismaleimide, and 3500 g (117 mmol) of polyetherketone material were thoroughly mixed by mechanical stirring. The mixture was then added to a twin-screw extruder and heated for melt blending. The feeding section temperature was 340 °C, the melting section temperature was 360 °C, and the discharge section temperature was 345 °C, resulting in a thermally reversible covalently bonded hyperbranched polymer-modified polyetherketone material. The modified polyetherketone material was then powdered and applied to selective laser sintering 3D printing.

[0054] Example 3: 65 g (5 mmol) of amino-terminated polyether ketone ketone hyperbranched polymer, 26.1 g (200 mmol) of furanoyl chloride, 1.22 g (10 mmol) of 4-dimethylaminopyridine (DMAP), and 12.65 g (125 mmol) of triethylamine were weighed and added to 600 mL of dichloromethane solvent. The mixture was reacted at room temperature for 24 hours with mechanical stirring. The reaction mixture was precipitated, filtered, washed, and dried to obtain furan-terminated polyether ketone ketone hyperbranched polymer. 100 g (6.2 mmol) of a hyperbranched polyetherketoneketone polymer with furan end groups, 111.1 g (310 mmol) of N,N'-(4,4'-methylenediphenyl)bismaleimide, and 20000 g (500 mmol) of polyetherketoneketone material were thoroughly mixed uniformly by mechanical stirring. The mixture was then added to a twin-screw extruder and heated for melt blending. The feeding section temperature was 340°C, the melting section temperature was 360°C, and the discharge section temperature was 350°C, yielding a hyperbranched polymer-modified polyetherketoneketone material containing thermally reversible covalent bonds. The modified polyetherketoneketone material was melt-extruded to obtain filaments, which were then applied to fused deposition modeling (FDM) 3D printing. See also... Figure 1 and 2 As can be seen, compared with the prior art, the material of the present invention has a smooth fracture surface and the layers are completely debonded, while the modified material has a rough and uneven fracture surface and the layers are bonded together.

[0055] Example 4: 60 g (4 mmol) of hydroxyl-terminated polyetheretherketone hyperbranched polymer, 31.3 g (240 mmol) of furanoyl chloride, 6.4 g (48 mmol) of anhydrous aluminum trichloride, and 600 mL of dichloromethane solvent were weighed and added to a 1000 mL three-necked flask. The mixture was ultrasonically mixed and dissolved, and reacted at 60 °C for 8 hours under N2 protection. After the reaction was completed and cooled, the mixture was added to deionized water to precipitate, filtered, washed successively with deionized water and ethanol, and dried to obtain furan-terminated polyetheretherketone hyperbranched polymer. Weigh 60 g (4 mmol) of hydroxyl-terminated polyetheretherketone hyperbranched polymer, 54.7 g (240 mmol) of maleimide hexanoyl chloride, and 5.3 g (40 mmol) of anhydrous aluminum trichloride, add them to 600 mL of dimethyl sulfoxide solvent, sonicate to dissolve, react at 60 °C for 12 hours under N2 protection, precipitate the reaction mixture, filter, wash, and dry to obtain maleimide-terminated polyetheretherketone hyperbranched polymer. 100 g (6.3 mmol) of furan-terminated polyetheretherketone (PEEEK) hyperbranched polymer, 102 g (6.3 mmol) of maleimide-terminated PEEEK hyperbranched polymer, and 2500 g (66 mmol) of PEEEK material were thoroughly mixed by mechanical stirring. The mixture was then added to a twin-screw extruder and heated for melt blending. The feeding section temperature was 345°C, the melting section temperature was 365°C, and the discharge section temperature was 350°C, resulting in a thermally reversible covalently bonded hyperbranched polymer-modified PEEK material. The modified PEEK material was melt-extruded to obtain filaments, which were then applied to fused deposition modeling (FDM) 3D printing.

[0056] Table 1 Mechanical properties of polyaryletherketone materials in the ZX direction (interlaminar direction)

[0057]

[0058] Descriptions of various advantageous arrangements have been shown for illustrative and descriptive purposes, but such descriptions are not intended to be exclusive or limited to the disclosed forms. Many modifications and variations will be apparent to those skilled in the art. Furthermore, different advantageous examples may describe different advantages compared to other advantageous examples. One or more examples have been selected and described in order to best illustrate the principles and practical application of the examples, and to enable those skilled in the art to understand that this disclosure contains various examples with various modifications suitable for the particular intended use.

Claims

1. A method for preparing a hyperbranched polymer-modified polyaryletherketone 3D printing material containing thermally reversible covalent bonds, characterized in that, Includes the following steps: Step 1: Obtaining hyperbranched polyaryletherketone polymers with furan end groups Hydroxyl-terminated polyaryletherketone hyperbranched polymer, furanoyl chloride, and anhydrous aluminum trichloride were added to dichloromethane solvent at a molar ratio of 1:30-60:8-12, and ultrasonically mixed and dissolved. Then, under an inert atmosphere, the reaction was kept at 50℃-80℃ for 4-8 hours to obtain furan-terminated polyaryletherketone hyperbranched polymer. In the hydroxyl-terminated polyaryletherketone hyperbranched polymer, the linear unit backbone includes aromatic groups, ether bonds and ketone bonds, and there is at least one ether bond or ketone bond between adjacent aromatic groups. Step 2: Mix the three components evenly. The first component is the polyaryletherketone hyperbranched polymer with furan end groups obtained in Step 1. The second component is a substance containing maleimide end groups. The third component is polyaryletherketone. When the second component is N,N'-(4,4'-methylenediphenyl)bismaleimide, N,N-m-phenylenebismaleimide or N,N'-tetramethylenebismaleimide, the molar ratio of the first component, the second component and the third component is 1:20 to 60:5 to 1000. When the second component is a maleimide-terminated polyaryletherketone hyperbranched polymer, the linear unit backbone of the maleimide-terminated polyaryletherketone hyperbranched polymer includes aromatic groups, ether bonds and ketone bonds, and there is at least one ether bond or ketone bond between adjacent aromatic groups; the molar ratio of the first component, the second component and the third component is 1:0.5 to 1.5:5 to 1000; Step 3: Heat, melt, and blend the three uniformly mixed substances to obtain a hyperbranched polymer-modified polyaryletherketone 3D printing material containing thermally reversible covalent bonds.

2. The method for preparing a thermally reversible covalently bonded hyperbranched polymer-modified polyaryletherketone 3D printing material as described in claim 1, characterized in that: The hydroxyl-terminated polyaryletherketone hyperbranched polymer is obtained by the following method: fluorine-terminated polyaryletherketone hyperbranched polymer, hydroquinone, anhydrous potassium carbonate, and anhydrous sodium carbonate are added to N-methylpyrrolidone solvent in a molar ratio of 1:50-80:3-6:6-12, and the mixture is ultrasonically mixed and dissolved. The mixture is then allowed to react fully for 8-12 hours at a temperature of 200℃-230℃ to obtain the hydroxyl-terminated polyaryletherketone hyperbranched polymer.

3. A method for preparing a hyperbranched polymer-modified polyaryletherketone 3D printing material containing thermally reversible covalent bonds, characterized in that, Includes the following steps: Step 1: Obtaining hyperbranched polyaryletherketone polymers with furan end groups Alkoxy-terminated polyaryletherketone hyperbranched polymer, furanoyl chloride, and anhydrous aluminum trichloride were added to dichloromethane solvent at a molar ratio of 1:30-60:8-12, and ultrasonically mixed and dissolved. Then, under an inert atmosphere, the reaction was carried out at 50℃-80℃ for 4-8 hours to obtain furan-terminated polyaryletherketone hyperbranched polymer. In the alkoxy-terminated polyaryletherketone hyperbranched polymer, the linear unit backbone includes aromatic groups, ether bonds and ketone bonds, and there is at least one ether bond or ketone bond between adjacent aromatic groups. Step 2: Mix the three components evenly. The first component is the polyaryletherketone hyperbranched polymer with furan end groups obtained in Step 1. The second component is a substance containing maleimide end groups. The third component is polyaryletherketone. When the second component is N,N'-(4,4'-methylenediphenyl)bismaleimide, N,N-m-phenylenebismaleimide or N,N'-tetramethylenebismaleimide, the molar ratio of the first component, the second component and the third component is 1:20 to 60:5 to 1000. When the second component is a maleimide-terminated polyaryletherketone hyperbranched polymer, the linear unit backbone of the maleimide-terminated polyaryletherketone hyperbranched polymer includes aromatic groups, ether bonds and ketone bonds, and there is at least one ether bond or ketone bond between adjacent aromatic groups; the molar ratio of the first component, the second component and the third component is 1:0.5 to 1.5:5 to 1000; Step 3: Heat, melt, and blend the three uniformly mixed substances to obtain a hyperbranched polymer-modified polyaryletherketone 3D printing material containing thermally reversible covalent bonds.

4. The method for preparing a hyperbranched polymer-modified polyaryletherketone 3D printing material containing thermally reversible covalent bonds as described in claim 3, characterized in that: The alkoxy-terminated polyaryletherketone hyperbranched polymer is obtained by the following steps: adding the fluorine-terminated polyaryletherketone hyperbranched polymer, the alkoxy nucleophile, and anhydrous potassium carbonate in an N-methylpyrrolidone solvent at a molar ratio of 1:50-80:4-8, mixing and dissolving by ultrasonication, and then reacting fully for 4-8 hours at a reaction temperature of 180℃-200℃ to obtain the alkoxy-terminated polyaryletherketone hyperbranched polymer.

5. A method for preparing a hyperbranched polymer-modified polyaryletherketone 3D printing material containing thermally reversible covalent bonds, characterized in that, Includes the following steps: Step 1: Obtaining hyperbranched polyaryletherketone polymers with furan end groups The amino-terminated polyaryletherketone hyperbranched polymer, furanoyl chloride, 4-dimethylaminopyridine (DMAP) and triethylamine were added to dichloromethane solvent at a molar ratio of 1:30-60:1-3:20-30 and mixed and dissolved. The mixture was then stirred for at least 24 hours to obtain the furan-terminated polyaryletherketone hyperbranched polymer. In the amino-terminated polyaryletherketone hyperbranched polymer, the linear unit backbone includes aromatic groups, ether bonds and ketone bonds, and there is at least one ether bond or ketone bond between adjacent aromatic groups. Step 2: Mix the three components evenly. The first component is the polyaryletherketone hyperbranched polymer with furan end groups obtained in Step 1. The second component is a substance containing maleimide end groups. The third component is polyaryletherketone. When the second component is N,N'-(4,4'-methylenediphenyl)bismaleimide, N,N-m-phenylenebismaleimide or N,N'-tetramethylenebismaleimide, the molar ratio of the first component, the second component and the third component is 1:20 to 60:5 to 1000. When the second component is a maleimide-terminated polyaryletherketone hyperbranched polymer, the linear unit backbone of the maleimide-terminated polyaryletherketone hyperbranched polymer includes aromatic groups, ether bonds and ketone bonds, and there is at least one ether bond or ketone bond between adjacent aromatic groups; the molar ratio of the first component, the second component and the third component is 1:0.5 to 1.5:5 to 1000; Step 3: Heat, melt, and blend the three uniformly mixed substances to obtain a hyperbranched polymer-modified polyaryletherketone 3D printing material containing thermally reversible covalent bonds.

6. The method for preparing a hyperbranched polymer-modified polyaryletherketone 3D printing material containing thermally reversible covalent bonds as described in claim 1, characterized in that: Maleimide-terminated polyaryletherketone hyperbranched polymers were obtained by the following method: hydroxyl-terminated polyaryletherketone hyperbranched polymers, maleimide hexanoic acid chloride, and anhydrous aluminum trichloride were added to dimethyl sulfoxide solvent at a molar ratio of 1:30-60:8-12 and mixed and dissolved. Then, under an inert atmosphere, the mixture was reacted at 50℃-80℃ for 8-12 hours to obtain maleimide-terminated polyaryletherketone hyperbranched polymers.

7. A method for preparing a hyperbranched polymer-modified polyaryletherketone 3D printing material containing thermally reversible covalent bonds as described in any one of claims 1-5, characterized in that: In maleimide-terminated polyaryletherketone hyperbranched polymers, the linear unit backbone is polyetherketone, polyetheretherketone, or polyetherketoneketone.

8. A method for preparing a hyperbranched polymer-modified polyaryletherketone 3D printing material containing thermally reversible covalent bonds as described in any one of claims 1-5, characterized in that: In step 1, the obtained furan-terminated polyaryletherketone hyperbranched polymer is subjected to precipitation, filtration, washing, and drying.

9. A method for preparing a hyperbranched polymer-modified polyaryletherketone 3D printing material containing thermally reversible covalent bonds as described in any one of claims 1-5, characterized in that: The temperature range for heating, melting, and blending in step 3 is 320℃~400℃.

10. A method for preparing a thermally reversible covalently bonded hyperbranched polymer-modified polyaryletherketone 3D printing material as described in any one of claims 1-5, characterized in that: The third component is one or more of polyetherketone, polyetheretherketone, polyetherketoneketone, and polyetheretherketoneketone.

11. A method for preparing a hyperbranched polymer-modified polyaryletherketone 3D printing material containing thermally reversible covalent bonds as described in any one of claims 1-5, characterized in that: The 3D printing material is suitable for fused deposition modeling (FDM) 3D printing, selective laser sintering (SLS) 3D printing, and layered solid manufacturing 3D printing.

12. A method for preparing a hyperbranched polymer-modified polyaryletherketone 3D printing material containing thermally reversible covalent bonds as described in any one of claims 1-5, characterized in that: In the furan-terminated polyaryletherketone hyperbranched polymer, the linear unit backbone is polyetherketone, polyetheretherketone, or polyetherketoneketone, with the following structural formulas: ， ， 。

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