Acrylate-based photosensitive hyperbranched poly(arylene ether ketone) and preparation method and application thereof

Abstract

The application discloses an acrylate-based photosensitive hyperbranched polyaryletherketone as well as a preparation method and application thereof. The preparation method comprises the following steps: sequentially adding trifluoromonomer, bisphenol monomer, salt-forming agent, organic solvent and water-carrying agent into a reactor in a protective gas atmosphere, carrying water for 2-5 hours at a temperature of 130 DEG C-150 DEG C, evaporating the water-carrying agent, and obtaining an intermediate product of polymerization reaction; then increasing the temperature of the reaction system to 160 DEG C-220 DEG C to carry out polymerization reaction for 10-24 hours, and stopping polymerization; then reducing the temperature of the reaction system to room temperature, adding a capping agent, increasing the temperature to 30 DEG C-50 DEG C to carry out capping reaction for 24-72 hours, then settling in a precipitant, and filtering, washing and drying to obtain the hyperbranched polyaryletherketone. The hyperbranched polyaryletherketone can be applied to formula design of 3D printing such as inkjet printing, ink direct writing technology and the like, and is more easy to be processed into complicated and precise sample pieces.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials, and specifically relates to an acrylate-based photosensitive hyperbranched polyarylether ketone, its preparation method, and its application. Background Technology

[0002] Photopolymer 3D printing technology has become a widely used rapid prototyping process due to its advantages such as high speed, high precision, and environmental friendliness. Photosensitive resin, a type of photosensitive polymer, is a major component in constructing the cross-linked network structure of 3D printed devices, and has a decisive influence on the device's performance and applications. The viscosity of the photosensitive resin has a significant impact on the resin's flowability during the molding process; lower viscosity is beneficial for improving printing speed and device precision.

[0003] Hyperbranched polymers are polymers with numerous branches and irregular structures, characterized by high functionality, good solubility, and low viscosity. Their synthesis is simple and does not require extensive purification. These characteristics make them suitable for industrial applications, particularly for photosensitive resins. For example, Chinese Patent 202211363707.X provides a low-viscosity UV-curable hyperbranched polyester acrylate, which not only has 100% solids content and low viscosity, but also requires only extremely low UV-LED curing energy (117.5 J / m) to form a film. The resulting film exhibits Grade 1 adhesion, good flexibility, high gloss, and high hardness. Furthermore, the preparation process is simple, allowing for mass production, and the double bond content of the resin is easily adjustable. Chinese Patent 202210378122.9 provides a photosensitive hyperbranched polyester used to manufacture polylactic acid (PLA) thin-walled injection molded products, which solves the problem of existing technologies failing to significantly improve the toughness of PLA products while simultaneously enhancing their flowability. Chinese Patent 202210393778.8 provides a hyperbranched conjugated polymer with excellent photosensitivity. Under light irradiation, it can efficiently generate various highly oxidizing reactive oxygen species, including singlet oxygen, superoxide anion radicals, and hydroxyl radicals. It can be used as a photosensitizer material in fields such as photodynamic therapy, photocatalytic oxidation reactions, wastewater treatment, and organic dyes.

[0004] However, the photosensitive prepolymers currently used in 3D printing are mainly aliphatic products such as polyurethane acrylate, polyester acrylate, and polyether acrylate. Although they have low viscosity, their poor heat resistance limits their applications, such as in the aerospace field. Poor heat resistance is also a major bottleneck restricting the development of photopolymer 3D printing technology. Therefore, there is a need to develop a photosensitive resin for 3D printing with high-temperature resistance and a long service life at high temperatures. Summary of the Invention

[0005] To address the problems existing in the prior art, the present invention provides an acrylate-based photosensitive hyperbranched polyarylether ketone, its preparation method, and its application.

[0006] The first aspect of the present invention provides an acrylate-based photosensitive hyperbranched polyaryletherketone, which has adjustable molecular weight, excellent photosensitivity, excellent thermal properties, and excellent solubility. It can be applied to the formulation design of 3D printing such as inkjet printing and direct ink writing technology, and is easier to process into complex and precise samples.

[0007] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0008] An acrylate-based photosensitive hyperbranched polyaryletherketone having the structure shown in formula (I) and / or formula (II);

[0009]

[0010] Where Ar is

[0011]

[0012] One of them; R is H or CH3.

[0013] In a preferred embodiment, the acrylate-based photosensitive hyperbranched polyaryletherketone has a number-average molecular weight of 2000-20000 g / mol (e.g., 3000 g / mol, 5000 g / mol, 7000 g / mol, 8000 g / mol, 10000 g / mol, 12000 g / mol, 15000 g / mol, 17000 g / mol, 18000 g / mol, or 19000 g / mol) and a glass transition. The temperature ranges from 120 to 260°C (e.g., 130°C, 150°C, 170°C, 190°C, 200°C, 220°C, 230°C, or 250°C), the initial weight loss temperature is 260 to 340°C (e.g., 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, or 330°C), and the 5% weight loss temperature is 380 to 470°C (e.g., 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, or 460°C).

[0014] The hyperbranched polyaryletherketone prepared by this invention has adjustable molecular weight, excellent photosensitivity, excellent thermal properties, and excellent solubility. It can be applied to the formulation design of 3D printing such as inkjet printing and direct ink writing technology, and is easier to process into complex and precise samples.

[0015] A second aspect of the present invention provides a method for preparing the above-mentioned acrylate-based photosensitive hyperbranched polyarylether ketone, wherein a trifluoro monomer and a bisphenol monomer are polymerized under alkaline catalysis in a polar solvent, and then a propionate group is introduced to prepare the acrylate-based photosensitive hyperbranched polyarylether ketone.

[0016] To achieve the above objectives, the present invention adopts the following technical solution.

[0017] A method for preparing acrylate-based photosensitive hyperbranched polyarylether ketone includes the following steps:

[0018] Trifluoro monomer, bisphenol monomer, salt-forming agent, organic solvent, and dehydrating agent are sequentially added to a reactor under a protective gas atmosphere (e.g., nitrogen or argon). The mixture is dehydrated at 130°C-150°C (e.g., 132°C, 135°C, 140°C, 145°C, or 148°C) for 2-5 hours (e.g., 2.5 hours, 3 hours, 3.5 hours, 4 hours, or 4.5 hours). The dehydrating agent is then distilled off to obtain the intermediate product of the polymerization reaction. The reaction system is then heated to 160°C-220°C (e.g., 165°C, 170°C, 180°C, 190°C, 200°C, or 210°C) to carry out polymerization. The polymerization is stopped after reacting for 10-24 hours (e.g., 11, 12, 15, 18, 20, 22, or 23 hours). The temperature of the reaction system is then lowered to room temperature, and a capping agent is added. The temperature is then raised to 30-50°C (e.g., 32, 35, 40, 45, or 48°C) for a capping reaction for 24-72 hours (e.g., 25, 30, 40, 50, 60, 65, or 70 hours). The product is then settled in a precipitant, filtered, washed, and dried to obtain the acrylate-based photosensitive hyperbranched polyaryletherketone product.

[0019] In this invention, taking 2,4',6-trifluorobenzophenone as an example, the chemical reaction principle of acrylate-based photosensitive hyperbranched polyarylether ketone is explained as follows:

[0020]

[0021] Where Ar is

[0022]

[0023] One of them; R is H or CH3.

[0024] In the above preparation method, as a preferred embodiment, the trifluoro monomer includes one of 2,4',6-trifluoro-benzophenone and 3,4',5-trifluoro-benzophenone; the molar ratio of the F functional group (or F atom) in the trifluoro monomer to the OH functional group in the bisphenol monomer is F:OH = 1:(1.33~2.0) (for example, 1:1.35, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8 or 1:1.9).

[0025] In the above preparation method, as a preferred embodiment, the bisphenol monomer includes at least one of hydroquinone, bisphenol A, hexafluorobisphenol A, bisphenol fluorene, spirocyclic bisphenol and 4-(4'-hydroxyphenyl)-2,3-diazanaphth-1-one (DHPZ).

[0026] In the above preparation method, as a preferred embodiment, the salt-forming agent is one or more of potassium carbonate, cesium carbonate, potassium hydroxide, sodium hydroxide, potassium hydride, and sodium hydride; further, the molar ratio of the metal cation in the salt-forming agent to the OH functional group in the bisphenol monomer is (1-1.2):1 (for example, 1.02:1, 1.05:1, 1.1:1, 1.15:1, or 1.18:1).

[0027] In the above preparation method, as a preferred embodiment, the organic solvent is one or more of N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide; furthermore, the ratio between the sum of the masses (g) of the trifluoro monomer and the bisphenol monomer and the volume (mL) of the organic solvent is (0.05-0.3):1 (e.g., 0.1:1, 0.15:1, 0.2:1, 0.25:1 or 0.28:1).

[0028] In the above preparation method, as a preferred embodiment, the dehydrating agent is one or more of benzene, toluene, xylene, and chlorobenzene; further, the volume ratio of the dehydrating agent to the organic solvent is 1:(0.5-3.5) (e.g., 1:0.8, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, or 1:3.3).

[0029] In the above preparation method, as a preferred embodiment, the precipitant is one or more of methanol, ethanol or water; further, the amount of the precipitant used is 0.25-2L (e.g., 0.3L, 0.5L, 0.8L, 1L, 1.5L or 1.8L).

[0030] In the above preparation method, as a preferred embodiment, the capping agent includes at least one of acryloyl chloride and methacryloyl chloride; the molar ratio of the capping agent to the phenolic hydroxyl group in the bisphenol monomer is (1-1.2):1 (e.g., 1.02:1, 1.05:1, 1.1:1, 1.15:1 or 1.18:1).

[0031] Preferably, in this invention, the room temperature is 15–30°C (e.g., 17°C, 20°C, 22°C, 25°C, or 28°C).

[0032] A third aspect of the present invention also provides the application of the above-mentioned acrylate-based photosensitive hyperbranched polyaryletherketone in the formulation design of 3D printing such as inkjet printing and direct ink writing technology.

[0033] In this invention, the preparation method of acrylate-based photosensitive hyperbranched polyarylether ketone starts from molecular structure design. First, by controlling the feeding ratio of trifluoro monomers to bisphenol monomers, polymerization temperature, and polymerization time, a hyperbranched polyarylether with adjustable molecular weight can be obtained. Second, different bisphenol structures, such as hydroquinone, bisphenol A, hexafluorobisphenol A, bisphenol fluorene, spirocyclic bisphenol, and 4-(4'-hydroxyphenyl)-2,3-diazanaphth-1-one, are introduced into the hyperbranched polyarylether prepolymer, which can impart strong rigidity to the polymer backbone and improve its heat resistance and mechanical properties. Finally, photocurable acrylate groups are introduced into the end groups, giving the polymer excellent photosensitivity. When applied to 3D printing formulations, this can significantly improve the curing rate and reduce the curing shrinkage rate.

[0034] In this invention, the above-mentioned technical features can be freely combined to form new technical solutions without conflict.

[0035] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0036] (1) The preparation method provided by the present invention can adjust the molecular weight of hyperbranched polyarylether ketone by controlling the feeding ratio of trifluoro monomer and bisphenol monomer, polymerization temperature and polymerization time; the number average molecular weight measured by gel permeation chromatography (GPC) is between 2000-20000 g / mol, and the intrinsic viscosity is between 0.05-0.15 dL / g (e.g. 0.07 dL / g, 0.09 dL / g, 0.10 dL / g, 0.12 dL / g or 0.14 dL / g), which can meet the needs of different occasions;

[0037] (2) The polyaryletherketone prepared by this invention is a series of aromatic polymers. Different bisphenol structures can give the polymer main chain strong rigidity and improve the heat resistance of the polymer. The glass transition temperature determined by differential scanning calorimetry (DSC) is between 120-260℃, the initial weight loss temperature is 260-340℃, and the 5% thermal weight loss temperature is 380-470℃.

[0038] (3) The polymer molecules prepared by this invention have a hyperbranched structure. The three-dimensional spatial structure similar to a sphere makes it possible for the molecules to be free of chain entanglement, thus giving it excellent solubility and making it easier to process into complex and precise devices.

[0039] (4) The hyperbranched polymer structure provided by the present invention contains a large number of acrylate end groups. When applied to 3D printing formulations, it can significantly improve the curing rate of the formulation and reduce the curing shrinkage rate. Attached Figure Description

[0040] Figure 1 The infrared spectrum of the acrylate-based photosensitive hyperbranched polyarylether ketone in Example 1 of this invention is shown.

[0041] Figure 2 The NMR spectrum of the acrylate-based photosensitive hyperbranched polyaryletherketone in Example 1 of this invention is shown.

[0042] Figure 3 This is the GPC spectrum of acrylate-based photosensitive hyperbranched polyaryletherketone in Example 1 of the present invention. Detailed Implementation

[0043] The technical solutions of the specific embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0044] Gel permeation chromatography (GPC) test conditions: performed on an Agilent 1260 instrument equipped with an ultraviolet (195–350 nm) detector, using N-methylpyrrolidone (NMP) as the solvent, with polystyrene as the standard sample for standard curve calibration, and the test temperature was 80 °C.

[0045] Differential scanning calorimetry (DSC) test conditions: performed on a Mettler DSC instrument, with a nitrogen flow rate of 50 mL / min and a heating rate of 20 °C / min.

[0046] Thermogravimetric (TG) test conditions: performed on a Mettler TGA instrument, with a nitrogen flow rate of 50 mL / min and a heating rate of 20 °C / min.

[0047] Intrinsic viscosity test conditions: The polymer was dissolved in N-methylpyrrolidone (NMP) to prepare a solution of 0.5 g / dL, and the intrinsic viscosity of the polymer was measured at 30°C using a Ubbelohde viscometer.

[0048] Example 1

[0049] Preparation of acrylate-based photosensitive hyperbranched polyaryletherketone 1

[0050] In a 250 mL three-necked flask equipped with a magnetic stirrer, a water-separating condenser, and a nitrogen inlet, 2,4',6-trifluorobenzophenone (4.7238 g, 20 mmol), hexafluorobisphenol A (14.1217 g, 42 mmol), potassium carbonate (6.9658 g, 50.4 mmol), N-methylpyrrolidone (130 mL), and toluene (50 mL) were added sequentially. The mixture was heated to 130 °C and reacted with water for 4 hours, after which the toluene was distilled off. The temperature was then raised to 180 °C, and the reaction was allowed to proceed for approximately 16 hours. After the reaction was complete and cooled to room temperature, 7 mL of acryloyl chloride was added, and the temperature was raised to 30 °C for end-capping reaction for 72 hours. Subsequently, the reactants were precipitated in 500 mL of deionized water. After filtration and washing with water, a light gray powdery polymer was obtained. The polymer was transferred to 500 mL of anhydrous ethanol and stirred at room temperature for approximately 1 hour. After filtration, the solid was dried in a forced-air oven at 80℃ to obtain a grayish-white powdered polymer: hb-P6FAEK26-Ace1.4, with a yield of approximately 89%. The infrared spectrum of the obtained product is shown below. Figure 1 The NMR spectrum of the obtained product is shown in [reference needed]. Figure 2 The GPC spectrum of the obtained product is shown in [reference needed]. Figure 3 The thermal properties, number-average molecular weight, and viscosity data are shown in Table 1, and the solubility properties are shown in Table 2.

[0051] Table 1. Thermal properties, molecular weight, and viscosity of the polymers in Examples 1-8

[0052]

[0053] a is the glass transition temperature; b is the initial decomposition temperature; c is the 5% weight loss temperature; d is the number-average molecular weight; e is the intrinsic viscosity.

[0054] Table 2 Solubility of polymers in Examples 1-8

[0055]

[0056] ++: Soluble at room temperature; +-: Soluble upon heating; --: Insoluble upon heating.

[0057] Example 2

[0058] Preparation of acrylate-based photosensitive hyperbranched polyaryletherketone 2

[0059] In a 250 mL three-necked flask equipped with a magnetic stirrer, a water-separating condenser, and a nitrogen inlet, 2,4',6-trifluorobenzophenone (4.7238 g, 20 mmol), bisphenol fluorene (14.7172 g, 42 mmol), potassium carbonate (6.9658 g, 50.4 mmol), N-methylpyrrolidone (130 mL), and toluene (50 mL) were added sequentially. The mixture was heated to 150 °C and reacted with water for 4 hours, after which the toluene was distilled off. The temperature was then raised to 180 °C, and the reaction was allowed to proceed for approximately 16 hours. After the reaction was complete and cooled to room temperature, 7 mL of acryloyl chloride was added, and the temperature was raised to 40 °C for end-capping reaction for 48 hours. Subsequently, the reactants were settled in 500 mL of deionized water. After filtration and repeated washing with water, a light gray powdery polymer was obtained. The polymer was transferred to 500 mL of anhydrous ethanol and stirred at room temperature for approximately 1 hour. After filtration, the solid was dried in a forced-air oven at 60℃ to obtain a grayish-white powdered polymer: hb-PFAEK26-Ace1.4, with a yield of approximately 84%. Thermal properties, number-average molecular weight, and viscosity data are shown in Table 1, and solubility properties are shown in Table 2.

[0060] Example 3

[0061] Preparation of acrylate-based photosensitive hyperbranched polyaryletherketone 3

[0062] In a 250 mL three-necked flask equipped with a magnetic stirrer, a water-separating condenser, and a nitrogen inlet, 2,4',6-trifluorobenzophenone (4.7238 g, 20 mmol), spirocyclobisphenol (18.4901 g, 60 mmol), potassium carbonate (9.9508 g, 72 mmol), N-methylpyrrolidone (150 mL), and toluene (50 mL) were added sequentially. The mixture was heated to 130 °C and reacted with water for 4 hours, after which the toluene was distilled off. The temperature was then raised to 200 °C, and the reaction was allowed to proceed for approximately 24 hours. After the reaction was complete and cooled to room temperature, 11 mL of acryloyl chloride was added, and the temperature was raised to 40 °C for end-capping reaction for 48 hours. Subsequently, the reactants were settled in 500 mL of deionized water. After filtration and repeated washing with water, a light gray powdery polymer was obtained. The polymer was transferred to 500 mL of anhydrous ethanol and stirred at room temperature for approximately 1 hour. After filtration, the solid was dried in an 80°C forced-air oven to obtain a grayish-white powder polymer: hb-PSAEK26-Ace2.0, with a yield of approximately 86%. Thermal properties, number-average molecular weight, and viscosity data are shown in Table 1, and solubility properties are shown in Table 2.

[0063] Example 4

[0064] Preparation of acrylate-based photosensitive hyperbranched polyaryletherketone 4

[0065] In a 250 mL three-necked flask equipped with a magnetic stirrer, a water-separating condenser, and a nitrogen inlet, 2,4',6-trifluorobenzophenone (4.7238 g, 20 mmol), bisphenol A (10.9577 g, 48 mmol), potassium carbonate (7.9601 g, 57.6 mmol), N-methylpyrrolidone (100 mL), and toluene (50 mL) were added sequentially. The mixture was heated to 130 °C and reacted with water for 4 hours, after which the toluene was distilled off. The temperature was then raised to 160 °C, and the reaction was allowed to proceed for approximately 16 hours. After the reaction was complete and cooled to room temperature, 8 mL of acryloyl chloride was added, and the temperature was raised to 50 °C for end-capping reaction for 24 hours. Subsequently, the reactants were settled in 500 mL of deionized water. After filtration and repeated washing with water, a light gray powdery polymer was obtained. The polymer was transferred to 500 mL of anhydrous ethanol and stirred at room temperature for approximately 1 hour. After filtration, the solid was dried in a forced-air oven at 40℃ to obtain a grayish-white powder polymer: hb-PBAEK26-Ace1.6, with a yield of approximately 86%. Thermal properties, number-average molecular weight, and viscosity data are shown in Table 1, and solubility properties are shown in Table 2.

[0066] Example 5

[0067] Preparation of acrylate-based photosensitive hyperbranched polyaryletherketone 5

[0068] In a 250 mL three-necked flask equipped with a magnetic stirrer, a water-separating condenser, and a nitrogen inlet, 2,4',6-trifluorobenzophenone (4.7238 g, 20 mmol), hydroquinone (6.6024 g, 60 mmol), potassium carbonate (9.9508 g, 72 mmol), N-methylpyrrolidone (80 mL), and toluene (50 mL) were added sequentially. The mixture was heated to 130 °C and reacted with water for 4 hours, after which the toluene was distilled off. The temperature was then raised to 160 °C, and the reaction was allowed to proceed for approximately 12 hours. After the reaction was complete and cooled to room temperature, 11 mL of acryloyl chloride was added, and the temperature was raised to 50 °C for end-capping reaction for 24 hours. Subsequently, the reactants were settled in 500 mL of deionized water. After filtration and repeated washing with water, a light gray powdery polymer was obtained. The polymer was transferred to 500 mL of anhydrous ethanol and stirred at room temperature for approximately 1 hour. After filtration, the solid was dried in a forced-air oven at 40°C to obtain a grayish-white powdered polymer: hb-PDAEK26-Ace2.0, with a yield of approximately 83%. Thermal properties, number-average molecular weight, and viscosity data are shown in Table 1, and solubility properties are shown in Table 2.

[0069] Example 6

[0070] Preparation of acrylate-based photosensitive hyperbranched polyaryletherketone 6

[0071] In a 250 mL three-necked flask equipped with a magnetic stirrer, a water-separating condenser, and a nitrogen inlet, 2,4',6-trifluorobenzophenone (4.7238 g, 20 mmol), 4-(4'-hydroxyphenyl)-2,3-diazanaphth-1-one (11.4274 g, 48 mmol), potassium carbonate (7.9601 g, 57.6 mmol), N-methylpyrrolidone (110 mL), and toluene (50 mL) were added sequentially. The mixture was heated to 130 °C and reacted with water for 4 hours, after which the toluene was distilled off. The temperature was then raised to 200 °C, and the reaction was allowed to proceed for approximately 16 hours. After the reaction was complete and cooled to room temperature, 8 mL of acryloyl chloride was added, and the temperature was raised to 40 °C for end-capping reaction for 48 hours. Subsequently, the reactants were settled in 500 mL of deionized water. After filtration and repeated washing with water, a light gray powdery polymer was obtained. The polymer was transferred to 500 mL of anhydrous ethanol and stirred at room temperature for about 1 h. After filtration, the solid was dried in an 80 °C oven to obtain a grayish-white powder polymer: hb-PZAEK26-Ace1.6, with a yield of about 85%. Thermal properties, number-average molecular weight, and viscosity data are shown in Table 1, and solubility properties are shown in Table 2.

[0072] Example 7

[0073] Preparation of acrylate-based photosensitive hyperbranched polyaryletherketone 7

[0074] In a 250 mL three-necked flask equipped with a magnetic stirrer, a water-separating condenser, and a nitrogen inlet, 3,4',5-trifluorobenzophenone (4.7238 g, 20 mmol), hexafluorobisphenol A (14.7172 g, 42 mmol), potassium carbonate (6.9658 g, 50.4 mmol), N-methylpyrrolidone (130 mL), and toluene (50 mL) were added sequentially. The mixture was heated to 130 °C and reacted with water for 4 hours, after which the toluene was distilled off. The temperature was then raised to 160 °C, and the reaction was allowed to proceed for approximately 16 hours. After the reaction was complete and cooled to room temperature, 7 mL of acryloyl chloride was added, and the temperature was raised to 30 °C for end-capping reaction for 72 hours. Subsequently, the reactants were settled in 500 mL of deionized water. After filtration and repeated washing with water, a light gray powdery polymer was obtained. The polymer was transferred to 500 mL of anhydrous ethanol and stirred at room temperature for approximately 1 hour. After filtration, the solid was dried in a forced-air oven at 40℃ to obtain a grayish-white powdered polymer: hb-P6FAEK35-Ace1.4, with a yield of approximately 86%. Thermal properties, number-average molecular weight, and viscosity data are shown in Table 1, and solubility properties are shown in Table 2.

[0075] Example 8

[0076] Preparation of acrylate-based photosensitive hyperbranched polyaryletherketone 8

[0077] In a 250 mL three-necked flask equipped with a magnetic stirrer, a water-separating condenser, and a nitrogen inlet, 3,4',5-trifluorobenzophenone (4.7238 g, 20 mmol), bisphenol A (9.5810 g, 42 mmol), potassium carbonate (6.9658 g, 50.4 mmol), N-methylpyrrolidone (100 mL), and toluene (50 mL) were added sequentially. The mixture was heated to 130 °C and reacted with water for 4 hours, after which the toluene was distilled off. The temperature was then raised to 160 °C, and the reaction was allowed to proceed for approximately 16 hours. After the reaction was complete and cooled to room temperature, 7 mL of acryloyl chloride was added, and the temperature was raised to 50 °C for end-capping reaction for 24 hours. Subsequently, the reactants were settled in 500 mL of deionized water. After filtration and repeated washing with water, a light gray powdery polymer was obtained. The polymer was transferred to 500 mL of anhydrous ethanol and stirred at room temperature for approximately 1 hour. After filtration, the solid was dried in a forced-air oven at 40℃ to obtain a grayish-white powder polymer: hb-PBAEK35-Ace1.4, with a yield of approximately 86%. Thermal properties, number-average molecular weight, and viscosity data are shown in Table 1, and solubility properties are shown in Table 2.

Claims

1. An acrylate-based photosensitive hyperbranched polyaryletherketone, characterized in that, It has the structure shown in formula (I) and / or formula (II); （I） （Ⅱ） Where Ar is R is H or CH3; The polyaryletherketone has a number-average molecular weight of 2000-20000 g / mol, an intrinsic viscosity of 0.05-0.15 dL / g, and a glass transition temperature of 120-260 °C. o C, the initial temperature of weightlessness is 260-340°C. o C, the temperature at which 5% thermal weight loss occurs is 380-470°C. o C.

2. A method for preparing acrylate-based photosensitive hyperbranched polyaryletherketone according to claim 1, characterized in that, The preparation method includes the following steps: Trifluoro monomer, bisphenol monomer, salt-forming agent, organic solvent, and dehydrating agent are sequentially added to a reactor under a protective gas atmosphere at a temperature of 130°C. o C-150 o Under temperature C, water is carried out for 2-5 hours, the water-carrying agent is evaporated, and the intermediate product of the polymerization reaction is obtained; then the temperature of the reaction system is raised to 160°C. o C-220 o The polymerization reaction is carried out at C for 10-24 hours, then stopped; the temperature of the reaction system is then lowered to room temperature, the end-capping agent is added, and the temperature is then raised to 30-50°C. o The end-capping reaction was carried out at C for 24-72 hours, and then the product was settled in a precipitant. After filtration, washing and drying, the acrylate-based photosensitive hyperbranched polyarylether ketone product was obtained.

3. The method for preparing acrylate-based photosensitive hyperbranched polyarylether ketone according to claim 2, characterized in that, The trifluoro monomer includes one of 2,4',6-trifluorobenzophenone and 3,4',5-trifluorobenzophenone; the bisphenol monomer is bisphenol fluorene; the end-capping agent includes at least one of acryloyl chloride and methacryl chloride; And / or, the salt-forming agent is one or more of potassium carbonate, cesium carbonate, potassium hydroxide, sodium hydroxide, potassium hydride, and sodium hydride; And / or, the organic solvent is one or more of N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide; And / or, the water-removing agent is one or more of benzene, toluene, xylene, and chlorobenzene; And / or, the precipitant is one or more of methanol, ethanol or water.

4. The method for preparing acrylate-based photosensitive hyperbranched polyaryletherketone according to claim 2 or 3, characterized in that, The molar ratio of the F functional group in the trifluoro monomer to the OH functional group in the bisphenol monomer is F : OH = 1 : (1.33~2.0); the molar ratio of the end-capping agent to the phenolic hydroxyl group in the bisphenol monomer is (1~1.2) :

1.

5. The method for preparing acrylate-based photosensitive hyperbranched polyaryletherketone according to claim 2 or 3, characterized in that, The molar ratio of the metal cation to the OH functional group in the bisphenol monomer in the salt-forming agent is (1~1.2):

1.

6. The method for preparing acrylate-based photosensitive hyperbranched polyaryletherketone according to claim 2 or 3, characterized in that, The ratio between the sum of the masses of the trifluoro monomer and the bisphenol monomer and the volume of the organic solvent is (0.05~0.3):1, where the unit of mass is g and the unit of volume is mL.

7. The method for preparing acrylate-based photosensitive hyperbranched polyaryletherketone according to claim 2 or 3, characterized in that, The volume ratio of the dehydrating agent to the organic solvent is 1:(0.5~3.5).

8. The method for preparing acrylate-based photosensitive hyperbranched polyarylether ketone according to claim 2 or 3, characterized in that, The amount of the precipitant used is 0.25L~2L.

9. The application of the acrylate-based photosensitive hyperbranched polyaryletherketone according to claim 1 or the acrylate-based photosensitive hyperbranched polyaryletherketone prepared by any one of claims 2-8 in 3D printing technology.

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