A small molecule photosensitive polyaryletherketone precursor, a preparation method and application thereof

Abstract

The application provides a small-molecule photosensitive polyaryletherketone precursor, a preparation method and application thereof, and belongs to the technical field of photosensitive resin and functional molecule synthesis. The application is designed from the photosensitivity of a small molecule. By regulating the photosensitivity of the small molecule, the polymerization of the small-molecule precursor with high molecular weight can be completed through photopolymerization. Meanwhile, the forming and curing problems of the small-molecule precursor can be further solved, and two goals are achieved at one time. The principle design of the application is different from the prior art scheme of realizing the photosensitivity of polyaryletherketone by using an oligomer. The prior art is difficult to realize good solubility, controllability of molecular weight and precise regulation of molecular structure, so that a polyaryletherketone photosensitive resin with good comprehensive performance cannot be prepared. The small-molecule photosensitive polyaryletherketone precursor obtained by the application has controllable molecular weight, controllable molecular structure, excellent photosensitivity and good solubility in active diluents and solvents.

Description

Technical Field

[0001] This invention relates to the field of photosensitive resin and functional molecule synthesis technology, and in particular to a small molecule photosensitive polyaryletherketone precursor, its preparation method and application. Background Technology

[0002] Polyaryletherketone (PAEK) is a high-performance engineering plastic composed of phenylene rings linked by ether and ketone bonds. Regularly structured PAEK is either crystalline or semi-crystalline. PAEK possesses excellent heat resistance, solvent resistance, abrasion resistance, hydrolysis resistance, radiation resistance, chemical resistance, impact resistance, and excellent fatigue resistance, placing it at the top of the resin performance pyramid and leading many to define it as a "perfect material." Due to its excellent corrosion resistance and tribological properties, it is widely used in aerospace, automotive manufacturing, and other industries, and its biocompatibility has led to its widespread application in biomedical implants.

[0003] Typical hydroquinone-based polyetheretherketone (PEEK) is mainly obtained by the stepwise polymerization of hydroquinone and 4,4-difluorobenzophenone at high temperatures. Generally, PEEK needs to be molded at high temperatures using methods such as injection molding, compression molding, and extrusion, followed by processing samples using traditional subtractive manufacturing processes such as milling, planing, and cutting. Considering the inherent strength of engineering plastics, strict selection of cutting tools and cutting speeds is necessary. Common PEEKs have a certain degree of crystallinity, resulting in low solubility in organic solvents, making solution processing difficult. Due to its poor solubility and refractory properties, existing molding and processing methods generally present problems, especially in the manufacture of complex lubricating components, where numerous limitations exist.

[0004] Photopolymerization technology utilizes ultraviolet light to initiate the rapid cross-linking and polymerization of chemically active liquid materials into solid materials, offering advantages such as fast curing and low energy consumption. Photocurable resins mainly consist of photosensitive precursors, reactive diluents, photoinitiators, and other additives, with the photosensitive precursor being the primary component and largely determining the performance of the cured resin. Current research on photopolymerization molding of high-performance resins primarily focuses on epoxy resins, phenolic resins, and polyimides. However, research on photosensitive polyaryletherketone resins is limited, and existing preparation methods typically involve first synthesizing polyaryletherketone oligomers and then attaching photosensitive groups to the molecular chain through the side or end groups of the oligomers. This approach suffers from problems such as poor photosensitivity and poor solubility of the oligomers themselves. Summary of the Invention

[0005] In view of this, the purpose of this invention is to provide a small-molecule photosensitive polyarylether ketone precursor, its preparation method, and its applications. The small-molecule photosensitive polyarylether ketone precursor provided by this invention exhibits good photosensitivity and excellent solubility.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] This invention provides a small-molecule photosensitive polyaryletherketone precursor having the structure shown in Formula I:

[0008]

[0009] Where R1 is * indicates a substitution site;

[0010] R2 is -H or -CH3;

[0011] R3 is

[0012] Preferably, the small molecule photosensitive polyaryletherketone precursor has a structure shown in any one of formulas A to E:

[0013]

[0014]

[0015] This invention also provides a method for preparing the small molecule photosensitive polyaryletherketone precursor described in the above technical solution, comprising the following steps:

[0016] A phenolic monomer, an acid-binding agent, and a solvent are mixed to obtain a mixed solution;

[0017] An acylation reaction is carried out by adding an acylation reagent dropwise to the mixed solution to obtain a monohydroxy aromatic phenol monomer, wherein the acylation reagent contains a photosensitive double bond;

[0018] The monohydroxy aromatic phenol monomer, difluorobenzophenone monomer and alkali metal catalyst were mixed and subjected to salt formation reaction and nucleophilic substitution reaction in sequence to obtain the small molecule photosensitive polyaryletherketone precursor.

[0019] The monohydroxy aromatic phenol monomer has the structure shown in Formula 1:

[0020]

[0021] In Equation 1, R1 is * indicates a substitution site;

[0022] R2 is either -H or -CH3.

[0023] Preferably, the phenolic monomer is p-aminophenol, m-aminophenol, 4-(4-aminophenyl)phenol, 4-(2-aminoethoxy)phenol, or 3-(2-aminoethyl)phenol.

[0024] Preferably, the acylation agent is acryloyl chloride, methacryloyl chloride, acrylic anhydride, or methacrylic anhydride.

[0025] Preferably, the acid-binding agent is triethylamine, sodium bicarbonate, sodium carbonate, or sodium hydroxide.

[0026] Preferably, the molar ratio of the phenolic monomer, the acid-binding agent, and the acylation reagent is 0.9–1.5:1–3:1.

[0027] Preferably, the acylation reaction is carried out at a temperature of 0–80°C for a time of 4–12 h.

[0028] Preferably, the molar ratio of the monohydroxy aromatic phenol monomer, the difluorobenzophenone monomer, and the alkali metal catalyst is 2-2.5:1:1-3.

[0029] The present invention also provides the application of the small molecule photosensitive polyaryletherketone precursor described in the above technical solution or the small molecule photosensitive polyaryletherketone precursor prepared by the preparation method described in the above technical solution in photosensitive polyaryletherketone resin.

[0030] This invention provides a small-molecule photosensitive polyaryletherketone precursor. Compared with the prior art, the advantages of this invention are as follows:

[0031] This invention starts with the design of photosensitivity of small molecules. By controlling the photosensitivity of small molecules, it enables the high molecular weight polymerization of small molecule precursors through photopolymerization. Simultaneously, it solves the problem of molding and curing small precursor molecules, achieving two goals at once. The principle of this invention differs from existing technologies that use oligomers to achieve photosensitivity in polyaryletherketones (PAKs). Existing technologies struggle to achieve good solubility, controllable molecular weight, and precise control of molecular structure, thus failing to prepare PAK photosensitive resins with good overall performance. In contrast, the small molecule photosensitive PAK precursor obtained by this invention has controllable molecular weight and tunable molecular structure, exhibiting excellent photosensitivity and good solubility in reactive diluents and solvents. This invention effectively solves the technical challenge of rapid photocuring of PAK materials from the aspects of molecular structure design and precise control, enabling innovative applications of small molecule PAK precursors as highly photosensitive resins in key technology fields such as photocurable 3D printing, nanoimprinting, biomedicine, electronic packaging, and low-temperature curing protective coatings.

[0032] This invention also provides a method for preparing the small-molecule photosensitive polyaryletherketone precursor described in the above technical solution. An acylation reagent with a photosensitive double bond is reacted with a phenolic monomer to obtain a photocurable monohydroxy aromatic phenolic monomer. This monomer is then reacted with a difluorobenzophenone monomer under catalytic conditions via a nucleophilic substitution reaction to obtain a small-molecule photosensitive polyaryletherketone precursor with high photosensitivity. Due to the small molecular weight preparation and precise control of the polyaryletherketone, its molecular activity is increased, thereby increasing its solubility and crystallinity. Therefore, the small-molecule photosensitive polyaryletherketone precursor provided by this invention exhibits good solubility in reactive diluents and solvents used in photocuring systems. Attached Figure Description

[0033] Figure 1 A physical image of the monohydroxy aromatic phenol monomer of Formula 2 prepared in Example 1;

[0034] Figure 2 The 1H NMR spectrum of the monohydroxy aromatic phenol monomer of Formula 2 prepared in Example 1;

[0035] Figure 3 The 1H NMR spectrum of the small molecule photosensitive polyaryletherketone precursor of Formula A prepared in Example 1;

[0036] Figure 4 A physical image of the solvent-free polyaryletherketone photosensitive resin prepared by mixing the small molecule photosensitive polyaryletherketone precursor of Formula A as described in Example 1 with an equal mass of N,N-dimethylacetamide and 1% phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0037] Figure 5 The image shows a physical photograph of the photocured polyaryletherketone film obtained from the solvent-free polyaryletherketone photosensitive resin in Example 1, with a light source wavelength of 405 nm, a light source intensity of 800 mW, and an exposure time of 5 s. Detailed Implementation

[0038] This invention provides a small-molecule photosensitive polyaryletherketone precursor having the structure shown in Formula I:

[0039]

[0040] Where R1 is * indicates a substitution site;

[0041] R2 is -H or -CH3;

[0042] R3 is

[0043] In this invention, the small molecule photosensitive polyarylether ketone precursor preferably has the structure shown in any one of formulas A to E:

[0044]

[0045]

[0046] This invention also provides a method for preparing the small molecule photosensitive polyaryletherketone precursor described in the above technical solution, comprising the following steps:

[0047] A phenolic monomer, an acid-binding agent, and a solvent are mixed to obtain a mixed solution;

[0048] An acylation reaction is carried out by adding an acylation reagent dropwise to the mixed solution to obtain a monohydroxy aromatic phenol monomer, wherein the acylation reagent contains a photosensitive double bond;

[0049] The monohydroxy aromatic phenol monomer, difluorobenzophenone monomer and alkali metal catalyst were mixed and subjected to salt formation reaction and nucleophilic substitution reaction in sequence to obtain the small molecule photosensitive polyaryletherketone precursor.

[0050] The monohydroxy aromatic phenol monomer has the structure shown in Formula 1:

[0051]

[0052] In Equation 1, R1 is * indicates a substitution site;

[0053] R2 is either -H or -CH3.

[0054] Unless otherwise specified, all raw materials used in this invention are commercially available products in the field.

[0055] This invention involves mixing phenolic monomers, acid-binding agents, and solvents to obtain a mixed solution.

[0056] In this invention, the phenolic monomer is preferably p-aminophenol, m-aminophenol, 4-(4-aminophenyl)phenol, 4-(2-aminoethoxy)phenol or 3-(2-aminoethyl)phenol, more preferably p-aminophenol, m-aminophenol or 4-(2-aminoethyl)phenol.

[0057] In this invention, the acid-binding agent is preferably triethylamine, sodium bicarbonate, sodium carbonate, or sodium hydroxide, and more preferably triethylamine or sodium bicarbonate.

[0058] In this invention, the solvent preferably includes one or more of water, dichloromethane, acetone, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, and more preferably one or more of water, dichloromethane and tetrahydrofuran.

[0059] The present invention does not impose any particular limitation on the specific method of mixing, and any method known to those skilled in the art can be used.

[0060] After obtaining the mixed solution, the present invention adds an acylation reagent dropwise to the mixed solution to carry out an acylation reaction to obtain a monohydroxy aromatic phenol monomer, wherein the acylation reagent contains a photosensitive double bond.

[0061] In this invention, the acylation is preferably acryloyl chloride, methacryloyl chloride, acrylic anhydride or methacrylic anhydride, more preferably acryloyl chloride or methacryloyl chloride.

[0062] In this invention, the molar ratio of the phenolic monomer, the acid-binding agent and the acylation reagent is preferably 0.9-1.5:1-3:1, more preferably 1-1.2:1.5-2:1.

[0063] In this invention, the temperature of the acylation reaction is preferably 0-80°C, more preferably 0-40°C, and most preferably room temperature. The time is preferably 4-12 hours, more preferably 6-10 hours. The time of the acylation reaction is calculated from the time the acylation reagent is completely added.

[0064] In this invention, the dropping rate is preferably such that the acylation reagent is added completely in 0.5 to 1 hour.

[0065] In this invention, if the obtained acylation product solution is a suspension, it is preferable to sequentially filter, wash and dry to obtain the monohydroxy aromatic phenol monomer; if the obtained acylation product solution is a solution, it is preferable to sequentially extract, concentrate under reduced pressure, filter, wash and dry to obtain the monohydroxy aromatic phenol monomer.

[0066] In this invention, the filtration and washing operations preferably use ultrapure water as the detergent and involve multiple cycles of washing and filtration.

[0067] In this invention, the drying process is preferably carried out by natural air drying at room temperature or freeze drying.

[0068] In a specific embodiment of the present invention, the monohydroxy aromatic phenol monomer preferably has the structure shown in the following formula:

[0069]

[0070] After obtaining the monohydroxy aromatic phenol monomer, the present invention mixes the monohydroxy aromatic phenol monomer, difluorobenzophenone monomer and alkali metal catalyst and sequentially carries out salt formation reaction and nucleophilic substitution reaction to obtain the small molecule photosensitive polyarylether ketone precursor.

[0071] In this invention, the molar ratio of the monohydroxy aromatic phenol monomer, the difluorobenzophenone monomer and the alkali metal catalyst is preferably 2-2.5:1:1-3, more preferably 2-2.2:1:1.2-2.

[0072] In this invention, the difluorobenzophenone monomer preferably includes one or more of 4,4-difluorobenzophenone, 1,4-bis(4-fluorobenzoyl)benzene, bis(4,1-phenylene)ether(4-fluorophenyl) ketone, 2,2-dipropane-bis(4,1-phenylene)bis(4-fluorophenyl) ketone, and (perfluoropropane-2,2-diyl)bis(4,1-phenylene)bis(4-fluorophenyl) ketone, more preferably 4,4-difluorobenzophenone.

[0073] In this invention, the alkali metal catalyst preferably includes one or more of potassium carbonate, sodium carbonate and lithium carbonate, more preferably potassium carbonate and / or sodium carbonate.

[0074] In this invention, the mixing process preferably further includes the addition of a solvent and a dehydrating agent. The solvent preferably includes one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, diphenyl sulfone, and sulfolane, more preferably one or more of N,N-dimethylformamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. The dehydrating agent preferably includes toluene and / or xylene, more preferably toluene.

[0075] In this invention, the obtained mixture is preferably heated to carry out the salt-forming reaction and the nucleophilic substitution reaction. The temperature of the salt-forming reaction is preferably 130-150°C, more preferably 140°C, and the time is preferably 2-5 hours, more preferably 3-4 hours. The temperature of the nucleophilic substitution reaction is preferably 140-200°C, more preferably 150-180°C, and the time is preferably 3-10 hours, more preferably 3-5 hours.

[0076] In this invention, the salt-forming reaction and nucleophilic substitution reaction are preferably carried out in an inert atmosphere, preferably nitrogen or argon. In a specific embodiment of this invention, the inert atmosphere is defined as the reaction system being stirred while an inert gas is passed through for 0.5 hours, followed by gradual heating to carry out the reaction, and the entire reaction system is maintained in an inert atmosphere until the reaction is complete.

[0077] After the salt formation reaction and nucleophilic substitution reaction are completed, the present invention preferably pours the product solution containing the small molecule photosensitive polyaryletherketone precursor into a precipitant to wash out the solid product, and then performs filtration, washing and drying in sequence to obtain the small molecule photosensitive polyaryletherketone precursor.

[0078] In this invention, the precipitant preferably includes one or more of water, methanol and ethanol, more preferably water or ethanol.

[0079] In this invention, the washing out of solid product preferably includes the following steps: pouring the product solution into a precipitant while it is still hot. In a specific embodiment of this invention, the filtration and washing operations preferably use hot water or hot ethanol as the washing agent, and perform multiple cycles of washing and filtration; the drying temperature is preferably 50°C, and the drying time is preferably 24 hours.

[0080] The present invention also provides the application of the small molecule photosensitive polyaryletherketone precursor described in the above technical solution or the small molecule photosensitive polyaryletherketone precursor prepared by the preparation method described in the above technical solution in photosensitive polyaryletherketone resin.

[0081] In this invention, the application preferably includes the following steps:

[0082] The small molecule photosensitive polyaryletherketone precursor, reactive diluent, solvent, photoinitiator and additives are mixed evenly to obtain a photocurable polyaryletherketone photosensitive resin for rapid prototyping.

[0083] In this invention, the reactive diluent preferably includes one or more of vinylformamide, vinylpyrrolidone, vinylcaprolactam, acrylomorpholine, and norborneol acrylate.

[0084] In this invention, the solvent preferably includes one or more of tetrahydrofuran, methylpyrrolidone, dimethylformamide, methylacetamide, ethyl acetate, 2-butanone, toluene, xylene, and cyclohexanone.

[0085] In this invention, the additives preferably include leveling agents and defoamers.

[0086] In this invention, the photoinitiator preferably includes one or more of the following: benzoin dimethyl ether, benzophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylphenylpropanone, and 2-isopropylthioxanthraphenone.

[0087] In this invention, the preferred mass ratio of the small molecule photosensitive polyaryletherketone precursor, reactive diluent, solvent, photoinitiator, and additive is 50:40:10:2:2.

[0088] In this invention, the polyaryletherketone photosensitive resin for photocurable rapid prototyping is preferably used in key technology fields such as high-performance photosensitive resins, photocurable 3D printing, nanoimprinting, electronic packaging, low-temperature curing protective coatings, and biomedicine.

[0089] This invention also provides the application of the aforementioned small molecule photosensitive polyaryletherketone precursor and photocurable polyaryletherketone photosensitive resin in photocurable 3D printing, printed circuit boards, and sealants.

[0090] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0091] Example 1

[0092] A monohydroxy aromatic phenol monomer with the structure of Formula 2 was prepared by means of the following method: 16.37 g of p-aminophenol, 20 g of sodium bicarbonate, 150 mL of water, and 150 mL of dichloromethane were added to a 500 mL three-necked flask under ice bath conditions, and the mixture was stirred for 0.5 h. Then, 14.93 g of acryloyl chloride, an acylation reagent with a photosensitive double bond, was added dropwise, with the addition controlled to be completed within 1 h. The ice bath was removed, and the reaction was allowed to proceed at room temperature for 6 h. After the reaction was completed, the mixture was filtered, and the filter cake was washed several times with ultrapure water and air-dried at room temperature to obtain 19.41 g of a monohydroxy aromatic phenol monomer with the structure of Formula 2, with a yield of 79.32%.

[0093]

[0094] A small-molecule photosensitive polyaryletherketone precursor with the structure shown in Formula A was prepared by means of the following method: 9.79 g of the monohydroxy aromatic phenol monomer described in Formula 2, 6.54 g of 4,4-difluorobenzophenone, 6.22 g of potassium carbonate, 60 g of N-methyl-2-pyrrolidone, and 30 g of toluene were stirred while nitrogen was purged for 0.5 h to ensure thorough mixing and removal of air from the reaction system. The mixture was then heated to 140 °C and held for 3 h to carry out a salt-forming reaction and remove water. The mixture was then heated to 160 °C and held for 3 h to carry out a nucleophilic substitution reaction. After the reaction was completed, the product solution was poured into a large amount of water while hot to wash out the solid product. The product was filtered, washed three times each with hot water and hot ethanol, and dried at 40 °C for 24 h to obtain the small-molecule photosensitive polyaryletherketone precursor with the structure shown in Formula A.

[0095]

[0096] Example 2

[0097] A monohydroxy aromatic phenol monomer with Formula 3 was prepared as follows: 5.46 g of m-aminophenol, 8.4 g of sodium bicarbonate, and 150 mL of tetrahydrofuran were added to a 250 mL three-necked flask under ice bath conditions, and the mixture was stirred for 0.5 h. Then, 4.53 g of acryloyl chloride, an acylation reagent with a photosensitive double bond, was added dropwise over 0.5 h. The ice bath was removed, and the reaction was allowed to proceed at room temperature for 10 h. After the reaction was complete, a large amount of ultrapure water was added to the reaction solution to separate the organic phase. The solution was dehydrated with anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, filtered again, washed repeatedly with ultrapure water, and air-dried at room temperature to obtain 5.57 g of a monohydroxy aromatic phenol monomer with Formula 3, with a yield of 68.23%.

[0098]

[0099] A small-molecule photosensitive polyaryletherketone precursor with the structure shown in Formula B was prepared by means of the following method: 19.6 g of a 3-monohydroxy aromatic phenol monomer, 13.1 g of 4,4-difluorobenzophenone, 12.44 g of potassium carbonate, 70 g of N-methyl-2-pyrrolidone, and 68 g of toluene were stirred while nitrogen was purged for 0.5 h to ensure thorough mixing and removal of air from the reaction system. The mixture was then heated to 140 °C and held for 4 h to carry out a salt-forming reaction and remove water. The mixture was then heated to 160 °C and held for 4 h to carry out a nucleophilic substitution reaction. After the reaction was completed, the product solution was poured into a large amount of water while hot to wash out the solid product. The product was filtered, washed three times each with hot water and hot ethanol, and dried at 40 °C for 24 h to obtain the small-molecule photosensitive polyaryletherketone precursor with the structure shown in Formula B.

[0100]

[0101] Example 3

[0102] A monohydroxy aromatic phenol monomer with the structure of Formula 2 was prepared by means of the following method: 32.74 g of p-aminophenol, 45 g of sodium bicarbonate, 320 mL of water, and 308 mL of dichloromethane were added to a 500 mL three-necked flask under ice bath conditions, and the mixture was stirred for 1 h. Then, 30.4 g of acryloyl chloride, an acylation reagent with a photosensitive double bond, was added dropwise, with the addition completed within 1 h. The ice bath was removed, and the reaction was allowed to proceed at room temperature for 7 h. After the reaction was complete, the mixture was filtered, and the filter cake was washed multiple times with ultrapure water and air-dried at room temperature to obtain 51.14 g of the monohydroxy aromatic phenol monomer with the structure of Formula 2, with a yield of 81%.

[0103] A small-molecule photosensitive polyaryletherketone precursor with the structure shown in Formula C was prepared by means of the following method: 19.58 g of the photosensitive monophenol monomer described in Formula 3, 19.34 g of 1,4-phenylenebis((4-fluorophenyl)methyl ketone), 12.44 g of potassium carbonate, 125 g of N-methyl-2-pyrrolidone, and 65 g of toluene were stirred while purging nitrogen gas for 1 h to ensure thorough mixing and removal of air from the reaction system. The mixture was then heated to 145 °C and held for 3.5 h to carry out a salt-forming reaction and remove water. The mixture was then heated to 160 °C and held for 4 h to carry out a nucleophilic substitution reaction. After the reaction was completed, the product solution was poured into a large amount of water while hot to wash out the solid product. The product was filtered, washed three times each with hot water and hot ethanol, and dried at 40 °C for 24 h to obtain the small-molecule photosensitive polyaryletherketone precursor with the structure shown in Formula C.

[0104]

[0105] Example 4

[0106] A monohydroxy aromatic phenol monomer with Formula 4 was prepared by means of the following method: 30.56 g of 2-methoxy-4-(2-aminoethyl)phenol, 25 g of sodium bicarbonate, 210 mL of water, and 180 mL of dichloromethane were added to a 500 mL three-necked flask under ice bath conditions, and the mixture was stirred for 1 h. Then, 14.93 g of acryloyl chloride, an acylation reagent with a photosensitive double bond, was added dropwise, with the addition completed over 1.5 h. The ice bath was removed, and the reaction was allowed to proceed at room temperature for 8 h. After the reaction was complete, the mixture was filtered, and the filter cake was washed several times with ultrapure water and air-dried at room temperature to obtain 37.43 g of a monohydroxy aromatic phenol monomer with Formula 4, with a yield of 82.3%.

[0107]

[0108] A small-molecule photosensitive polyaryletherketone precursor with the structure shown in Formula D was prepared by means of the following method: 14.59 g of a monohydroxy aromatic phenol monomer of Formula 4, 6.54 g of 4,4-difluorobenzophenone, 6.45 g of potassium carbonate, 80 g of N-methyl-2-pyrrolidone, and 40 g of toluene were stirred while purging nitrogen gas for 1.5 h to ensure thorough mixing and removal of air from the reaction system. The mixture was then heated to 140 °C and held for 5 h to carry out a salt-forming reaction and remove water. The mixture was then heated to 160 °C and held for 6 h to carry out a nucleophilic substitution reaction. After the reaction was completed, the product solution was poured into a large amount of water while hot to wash out the solid product. The product was filtered, washed three times each with hot water and hot ethanol, and dried at 40 °C for 24 h to obtain the small-molecule photosensitive polyaryletherketone precursor with the structure shown in Formula D.

[0109]

[0110] Example 5

[0111] The method for preparing monohydroxy aromatic phenol monomers having the structure of Formula 5 is as follows:

[0112] Under ice bath conditions, 10.95 g of m-aminophenol, 17.3 g of sodium bicarbonate, and 310 mL of tetrahydrofuran were added to a 500 mL three-necked flask and stirred for 1 h. Then, 10.24 g of methacryloyl chloride, an acylation reagent with a photosensitive double bond, was added dropwise over 1 h. The ice bath was removed, and the reaction was allowed to proceed at room temperature for 8 h. After the reaction was complete, a large amount of ultrapure water was added to the reaction solution to separate the organic phase. The solution was dehydrated with anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, filtered again, washed multiple times with ultrapure water, and air-dried at room temperature to obtain 14.8 g of a monohydroxy aromatic phenol monomer with the structure of formula 5, with a yield of 70%.

[0113]

[0114] A small-molecule photosensitive polyaryletherketone precursor with the structure shown in Formula E was prepared by means of the following method: 21.28 g of a 5-monohydroxy aromatic phenol monomer, 26.2 g of 4,4-difluorobenzophenone, 25.4 g of potassium carbonate, 145 g of N-methyl-2-pyrrolidone, and 138 g of toluene were stirred while nitrogen was purged for 0.5 h to ensure thorough mixing and removal of air from the reaction system. The mixture was then heated to 145 °C and held for 4 h to carry out a salt-forming reaction and remove water. The mixture was then heated to 168 °C and held for 4 h to carry out a nucleophilic substitution reaction. After the reaction was completed, the product solution was poured into a large amount of water while hot to wash out the solid product. The product was filtered, washed three times each with hot water and hot ethanol, and dried at 40 °C for 24 h to obtain the small-molecule photosensitive polyaryletherketone precursor with the structure shown in Formula E.

[0115]

[0116] Figure 1 A physical image of the monohydroxy aromatic phenol monomer of Formula 2 prepared in Example 1; Figure 2 The 1H NMR spectrum of the monohydroxy aromatic phenol monomer of Formula 2 prepared in Example 1; Figure 3 The 1H NMR spectrum of the small molecule photosensitive polyaryletherketone precursor of Formula A prepared in Example 1.

[0117] The small-molecule photosensitive polyaryletherketone precursor of formula A obtained in Example 1 was mixed with an equal mass of N,N-dimethylacetamide and 1% by mass of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide to obtain a solvent-free polyaryletherketone photosensitive resin. Figure 4 The image shows a physical picture of the solvent-free polyaryletherketone photosensitive resin. It can be seen that the small molecule photosensitive polyaryletherketone precursor of the present invention has good solubility in the reactive diluent, and the resulting solvent-free polyaryletherketone photosensitive resin has low viscosity.

[0118] Figure 5The image shows a physical picture of a photocurable polyaryletherketone (PAEK) film obtained by solvent-free PAEK photosensitive resin under light source wavelength of 405 nm, light source intensity of 800 mW, and exposure time of 5 s. It can be seen that the small molecule photosensitive PAEK precursor of the present invention has good photosensitivity, and the obtained photosensitive resin has good photocuring performance, which also illustrates the photocurable molding function of PAEK material.

[0119] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A small molecule photosensitive polyaryletherketone precursor, characterized in that, It has the structure shown in any one of the terms A to E: Formula A Formula B Formula C Formula D Formula E.

2. The method for preparing the small molecule photosensitive polyaryletherketone precursor according to claim 1, characterized in that, Includes the following steps: A phenolic monomer, an acid-binding agent, and a solvent are mixed to obtain a mixed solution; An acylation reaction is carried out by adding an acylation reagent dropwise to the mixed solution to obtain a monohydroxy aromatic phenol monomer, wherein the acylation reagent contains a photosensitive double bond; The monohydroxy aromatic phenol monomer, difluorobenzophenone monomer and alkali metal catalyst were mixed and subjected to salt formation reaction and nucleophilic substitution reaction in sequence to obtain the small molecule photosensitive polyaryletherketone precursor. The monohydroxy aromatic phenol monomer has the structure shown in Formula 1: Formula 1, In Equation 1, R1 is , or , For substitution sites; R2 is either -H or -CH3.

3. The preparation method according to claim 2, characterized in that, The phenolic monomer is p-aminophenol, m-aminophenol, or 2-methoxy-4-(2-aminoethyl)phenol.

4. The preparation method according to claim 2, characterized in that, The acylation reagent is acryloyl chloride, methacryloyl chloride, acrylic anhydride, or methacrylic anhydride.

5. The preparation method according to claim 2, characterized in that, The acid-binding agent is triethylamine, sodium bicarbonate, sodium carbonate, or sodium hydroxide.

6. The preparation method according to any one of claims 2 to 5, characterized in that, The molar ratio of the phenolic monomer, acid-binding agent, and acylation reagent is 0.9~1.5:1~3:

1.

7. The preparation method according to claim 2, characterized in that, The acylation reaction is carried out at a temperature of 0~80℃ for a time of 4~12h.

8. The preparation method according to claim 2, characterized in that, The molar ratio of the monohydroxy aromatic phenol monomer, the difluorobenzophenone monomer, and the alkali metal catalyst is 2~2.5:1:1~3.

9. The application of the small molecule photosensitive polyaryletherketone precursor according to claim 1 or the small molecule photosensitive polyaryletherketone precursor prepared by any one of claims 2 to 8 in the preparation of photosensitive polyaryletherketone resin.

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