Ultraviolet light-cured resin, preparation method and application thereof

Abstract

The application provides an ultraviolet light curing resin and a preparation method and application thereof. The preparation method of the ultraviolet light curing resin comprises the following steps: preparing a prepolymer, carrying out prepolymerization reaction on a perfluoropolyether derivative containing an acrylate functional group and a phosphate functional monomer at 60-80 DEG C to obtain the prepolymer; preparing a resin body, carrying out click chemistry reaction on the prepolymer and a multi-functional sulfur at 50-55 DEG C to obtain the resin body; and preparing a target product, mixing the resin body with a photoinitiator and an active diluent to obtain the ultraviolet light curing resin. The preparation method is simple in process and mild in condition, does not need a heavy metal catalyst, and the prepared resin is excellent in adhesion and outstanding in acid and alkali resistance.

Description

Technical Field

[0001] This application belongs to the field of polymer materials technology, and in particular relates to a method for preparing an ultraviolet-curable resin and its application. Background Technology

[0002] UV-curable resins are widely used in coatings, adhesives, inks, and electronic packaging due to their advantages such as fast curing speed, low energy consumption, and environmental friendliness. However, traditional UV-curable resins have significant shortcomings in acid and alkali resistance and adhesion. For example, they are prone to performance degradation in acidic or alkaline corrosive environments, have insufficient adhesion to substrates such as metals and glass, and resin coatings are prone to swelling, peeling, and loss of gloss, seriously affecting their service life and reliability.

[0003] In existing technologies, methods for improving the acid and alkali resistance and adhesion of resins mainly include physical blending and chemical modification. While chemical modification methods, such as introducing polar groups and cross-linking structures, can partially improve performance, the modification processes are often complex, making it difficult to achieve a performance balance, requiring harsh reaction conditions, and frequently using harmful catalysts. For example, CN102120123A uses epoxy resin modification, which improves adhesion, but the acid and alkali resistance is still unsatisfactory; CN101735689A improves adhesion by introducing silane coupling agents, but the synthesis process requires heavy metal catalysts, which does not meet environmental protection requirements.

[0004] Therefore, developing a UV-curable resin that is simple to process, environmentally friendly, and has both high adhesion and excellent acid and alkali resistance has significant industrial application value and market prospects. Summary of the Invention

[0005] The purpose of this application is to provide a UV-curable resin, its preparation method and application, aiming to solve the problems of complex chemical modification process conditions, frequent use of harmful catalysts and poor acid and alkali resistance of products in the prior art.

[0006] To achieve the above-mentioned objectives, the technical solution adopted in this application is as follows: In a first aspect, this application provides a method for preparing a UV-curable resin, comprising the following steps: The raw materials provided include: perfluoropolyether derivatives containing acrylate functional groups, phosphate functional monomers, multifunctional thiol crosslinking agents, photoinitiators, and reactive diluents; The perfluoropolyether derivative containing acrylate functional groups is subjected to a prepolymerization reaction with the phosphate functional monomer at 60-80°C to obtain a prepolymer. The prepolymer and the multifunctional thiol crosslinking agent are subjected to a click chemical reaction at 50-55°C to obtain the resin matrix. The resin bulk is mixed with the photoinitiator and the reactive diluent to obtain a UV-curable resin.

[0007] The UV-curable resin preparation method of this application introduces a fluorinated raw material, perfluoropolyether, which significantly enhances the resin's resistance to acid and alkali corrosion by utilizing the low surface energy and chemical inertness of fluorine atoms. Simultaneously, phosphate ester groups are introduced, which improve the resin's adhesion to substrates such as metals and glass by forming strong coordination bonds or hydrogen bonds with the substrate. A click chemistry reaction (thiol-alkene radical addition reaction) is employed to achieve the formation of a branched structure under mild conditions. This method is applicable to industrial fields with stringent material performance requirements, such as electronic packaging, metal protective coatings, and high-precision printing, and is particularly suitable for protective coatings of precision devices that require long-term exposure to corrosive environments.

[0008] In some embodiments, the total mass of the raw materials is 100%, and the perfluoropolyether derivative containing acrylate functional groups accounts for 20-40% of the total mass of the raw materials; And / or, the phosphate ester functional monomer accounts for 10-20% of the total mass of the raw material; And / or, the multifunctional thiol crosslinking agent accounts for 5-15% of the total mass of the raw materials; And / or, the photoinitiator accounts for 1-3% of the total mass of the raw materials.

[0009] In some embodiments, the perfluoropolyether derivative containing acrylate functional groups includes at least one of perfluoropolyether acrylate, perfluoropolyether methacrylate, and perfluoropolyether ethyl acrylate.

[0010] In some embodiments, the prepolymerization reaction is carried out in an anaerobic environment; and / or, the prepolymerization reaction takes 1-2 hours. Preferably, the prepolymerization reaction is carried out in an inert gas protected environment.

[0011] In some embodiments, the phosphate functional monomer includes at least one of hydroxyethyl phosphate and methacrylate phosphate; And / or, the multifunctional thiol crosslinking agent includes at least one of pentaerythritol tetra(3-mercaptopropionate) and trimethylolpropane tri(3-mercaptopropionate).

[0012] In some embodiments, the photoinitiator includes at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone and 1-hydroxycyclohexylphenyl ketone; And / or, the reactive diluent includes at least one of isoborneol acrylate, lauryl acrylate, and hydroxyethyl acrylate.

[0013] Secondly, this application provides a UV-curable resin, wherein the raw materials for preparing the UV-curable resin include the following components in parts by weight: Perfluoropolyether derivatives containing acrylate functional groups: 20-40 parts; Phosphate ester functional monomers: 10-20 parts; Multifunctional thiol crosslinking agent: 5-15 parts; Photoinitiator: 1-3 parts; Reactive diluent: Used to bring the total mass fraction of raw materials to 100 parts.

[0014] In some embodiments, the perfluoropolyether derivative containing acrylate functional groups includes at least one of perfluoropolyether acrylate, perfluoropolyether methacrylate, and perfluoropolyether ethyl acrylate. And / or, the phosphate ester functional monomer includes at least one of hydroxyethyl phosphate ester and methacrylate phosphate ester; And / or, the multifunctional thiol crosslinking agent includes at least one of pentaerythritol tetra(3-mercaptopropionate) and trimethylolpropane tri(3-mercaptopropionate); And / or, the photoinitiator includes at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone and 1-hydroxycyclohexylphenyl ketone; And / or, the reactive diluent includes at least one of isoborneol acrylate, lauryl acrylate, and hydroxyethyl acrylate.

[0015] In some embodiments, the UV-curable resin is prepared by the above-described preparation method.

[0016] Thirdly, the application of at least one of the ultraviolet-curable resins prepared by the preparation method described in the first aspect of this application or the ultraviolet-curable resins described in the second aspect in the fields of electronic packaging, metal protection and high-precision printing.

[0017] The UV-curable resin prepared by the first method has the advantages of excellent adhesion, outstanding acid and alkali resistance, fast curing speed and high hardness, and has important industrial application value and market prospects in the fields of electronic packaging, metal protective coating and high-precision printing.

[0018] Compared with the prior art, the beneficial effects of this application are as follows: 1. The preparation method of this application is simple and mild, does not require heavy metal catalysts, and meets the requirements of green chemistry; it adopts click chemistry reaction (thiol-alkene radical addition reaction) to achieve rapid and highly selective polymerization.

[0019] 2. The resin prepared using the method of this application exhibits excellent adhesion, achieving grade 0 in the cross-cut test; it demonstrates outstanding acid and alkali resistance, remaining unaffected after immersion in 10% H2SO4 and 10% NaOH solutions for 24 hours; it cures rapidly, with a curing time ≤35 seconds under 365nm ultraviolet light; it possesses high hardness, achieving a pencil hardness of H-2H; it has a high gel content (≥94.8%), a complete cross-linking network, and excellent solvent resistance.

[0020] 3. The resin prepared by the method of this application has significant industrial application value and market prospects, and has a wide range of applications, including electronic packaging, metal protective coating, high-precision printing and other fields. Detailed Implementation

[0021] To make the technical problems, technical solutions, and beneficial effects of this application clearer, the following detailed description is provided in conjunction with embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0022] In this application, the term "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0023] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0024] It should be understood that in the various embodiments of this application, the order of the above processes does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.

[0025] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. The singular forms “a,” “the,” and “the” used in the embodiments of this application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.

[0026] The weights of the relevant components mentioned in the embodiments of this application can refer not only to the specific content of each component, but also to the proportional relationship between the weights of the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments of this application is within the scope disclosed in the embodiments of this application. Specifically, the mass described in the embodiments of this application can be a well-known unit of mass in the chemical industry, such as µg, mg, g, or kg.

[0027] The first aspect of this application provides a method for preparing a UV-curable resin, comprising the following steps: S01: Provide raw materials, the raw materials including: perfluoropolyether derivatives containing acrylate functional groups, phosphate functional monomers, multifunctional thiol crosslinking agents, photoinitiators and reactive diluents; S02: Prepolymer preparation involves reacting a perfluoropolyether derivative containing acrylate functional groups with a phosphate functional monomer at 60-80°C to obtain the prepolymer. S03: Prepare the resin body. After the prepolymerization reaction is completed, cool the reaction system to 50-55°C and add a multifunctional thiol crosslinking agent. The prepolymer and the multifunctional thiol crosslinking agent undergo a click chemical reaction to obtain the resin body. S04: To prepare the target product, the resin bulk is mixed with a photoinitiator and an active diluent to obtain the UV-curable resin.

[0028] The UV-curable resin preparation method of this application introduces a fluorinated raw material, perfluoropolyether, which significantly enhances the resin's resistance to acid and alkali corrosion by utilizing the low surface energy and chemical inertness of fluorine atoms. Simultaneously, phosphate ester groups are introduced, which improve the resin's adhesion to substrates such as metals and glass by forming strong coordination bonds or hydrogen bonds with the substrate. A click chemistry reaction (thiol-alkene radical addition reaction) is employed to achieve the formation of a branched structure under mild conditions. This method is applicable to industrial fields with stringent material performance requirements, such as electronic packaging, metal protective coatings, and high-precision printing, and is particularly suitable for protective coatings of precision devices that require long-term exposure to corrosive environments.

[0029] The raw materials used in the preparation method of this application include perfluoropolyether derivatives containing acrylate functional groups, phosphate functional monomers, multifunctional thiol crosslinking agents, photoinitiators, and reactive diluents.

[0030] In some embodiments, based on the total mass of the above raw materials as 100%, the perfluoropolyether derivative containing acrylate functional groups accounts for 20-40% of the total mass of the raw materials. Exemplarily, this can be any of the above values ​​or within any combination of both, such as 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%. In some embodiments, the phosphate ester functional monomer accounts for 10-20% of the total mass of the raw materials. Exemplarily, this can be any of the above values ​​or within any combination of both, such as 10%, 12%, 14%, 15%, 17%, 18%, 20%. In some embodiments, the multifunctional thiol crosslinking agent accounts for 5-15% of the total mass of the raw materials. Exemplarily, this can be any of the above values ​​or within any combination of both, such as 5%, 6%, 7.5%, 9%, 10%, 12%, 14%, 15%. In some embodiments, the photoinitiator accounts for 1-3% of the total mass of the raw materials. For example, it can be any of the above values ​​or within any range of both, such as 1%, 1.2%, 1.5%, 1.8%, 2%, 2.4%, 2.8%, 3%.

[0031] In some embodiments, based on the total mass of the above raw materials (100%), the perfluoropolyether derivative containing acrylate functional groups accounts for 20-40% of the total raw material mass, the phosphate ester functional monomer accounts for 10-20% of the total raw material mass, the multifunctional thiol crosslinking agent accounts for 5-15% of the total raw material mass, the photoinitiator accounts for 1-3% of the total raw material mass, and the balance is the reactive diluent. Under the above proportions, performance balance can be achieved by adjusting the mass ratio of each raw material, resulting in a high-performance UV-curable resin under mild reaction conditions.

[0032] In some embodiments, the perfluoropolyether derivative containing acrylate functional groups includes at least one of perfluoropolyether acrylate, perfluoropolyether methacrylate, and perfluoropolyether ethyl acrylate. This application introduces perfluoropolyether, a fluorinated raw material, and utilizes the low surface energy and chemical inertness of fluorine atoms to significantly improve the resin's resistance to acid and alkali corrosion.

[0033] In some embodiments, the prepolymerization reaction is carried out in an oxygen-free environment. Preferably, the prepolymerization reaction is carried out in an environment protected by an inert gas.

[0034] In some embodiments, the phosphate ester functional monomer includes at least one of hydroxyethyl acrylate and methacrylate. This application introduces phosphate ester groups to improve the adhesion of the resin to substrates such as metals and glass by forming strong coordination bonds or hydrogen bonds with the substrate.

[0035] In some embodiments, the multifunctional thiol crosslinking agent includes at least one of pentaerythritol tetra(3-mercaptopropionate) and trimethylolpropane tri(3-mercaptopropionate). This application employs click chemistry to achieve rapid, highly selective polymerization under mild conditions, without the need for heavy metal catalysts, making it environmentally friendly.

[0036] In some embodiments, the photoinitiator includes at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone and 1-hydroxycyclohexylphenyl methyl ketone.

[0037] In some embodiments, the reactive diluent includes at least one of isoborneol acrylate, lauryl acrylate, and hydroxyethyl acrylate.

[0038] In some embodiments, the preparation of the prepolymer includes the step of: subjecting a perfluoropolyether derivative containing acrylate functional groups to a phosphate functional monomer for a prepolymerization reaction at 60-80°C for 1-2 hours to obtain the prepolymer.

[0039] In some embodiments, the preparation of the resin bulk includes the steps of: cooling the system to 50-55°C after the prepolymerization reaction, then adding a multifunctional thiol crosslinking agent, and performing a click chemistry reaction with the prepolymer for 30-60 minutes until the thiol characteristic peak (2570 cm⁻¹) is reached. - ¹) The reaction disappears, yielding the resin matrix. Based on the principle of click chemistry, the key reaction is completed in a low-temperature range of 50-55℃, reducing side reactions and ensuring the structural regularity and performance consistency of the product. Moreover, the click chemistry reaction achieves rapid and highly selective polymerization under mild conditions, without the need for heavy metal catalysts, making it green and environmentally friendly.

[0040] In some embodiments, the preparation of the target product includes the steps of: homogenizing and mixing the resin bulk, photoinitiator, and reactive diluent to obtain the UV-curable resin, and storing it in the dark. Specifically, after homogenization and mixing, the resin is aged in the dark to obtain the target resin.

[0041] Secondly, a UV-curable resin is provided. Specifically, the raw materials for preparing the UV-curable resin with high adhesion and acid / alkali resistance of this application comprise the following components in parts by weight: Perfluoropolyether derivatives containing acrylate functional groups: 20-40 parts; Phosphate ester functional monomers: 10-20 parts; Multifunctional thiol crosslinking agent: 5-15 parts; Photoinitiator: 1-3 parts; Reactive diluent: Used to bring the total mass fraction of raw materials to 100 parts.

[0042] Among the above components, perfluoropolyether derivatives containing acrylate functional groups are introduced, utilizing the low surface energy and chemical inertness of fluorine atoms to significantly enhance the resin's resistance to acid and alkali corrosion. Phosphate groups are introduced, forming strong coordination bonds or hydrogen bonds with the substrate, thereby improving the resin's adhesion to metal, glass, and other substrates. Through the combined effect of these components, the UV-curable resin of this application possesses advantages such as high adhesion and excellent acid and alkali resistance, making it suitable for industrial fields with stringent material performance requirements, such as electronic packaging, metal protective coatings, and high-precision printing. It is particularly suitable for protective coatings of precision devices that require long-term exposure to corrosive environments.

[0043] In some embodiments, the perfluoropolyether derivative containing acrylate functional groups includes at least one of perfluoropolyether acrylate, perfluoropolyether methacrylate, and perfluoropolyether ethyl acrylate. The phosphate functional monomer includes at least one of hydroxyethyl phosphate acrylate and methacrylate. The multifunctional thiol crosslinking agent includes at least one of pentaerythritol tetra(3-mercaptopropionate) and trimethylolpropane tri(3-mercaptopropionate). The photoinitiator includes at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone and 1-hydroxycyclohexylphenyl ketone. The reactive diluent includes at least one of isobornyl acrylate, lauryl acrylate, and hydroxyethyl acrylate.

[0044] In some embodiments, the UV-curable resin of this application is prepared by the above-described preparation method.

[0045] Thirdly, the application of at least one of the ultraviolet-curable resins prepared by the preparation method described in the first aspect of this application or the ultraviolet-curable resins described in the second aspect in the fields of electronic packaging, metal protection and high-precision printing.

[0046] The UV-curable resin of this application has the advantages of excellent adhesion, outstanding acid and alkali resistance, fast curing speed, and high hardness. Specifically, the resin has excellent adhesion, achieving a grade of 0 in the cross-cut adhesion test; it has outstanding acid and alkali resistance, remaining unaffected after immersion in 10% H2SO4 and 10% NaOH solutions for 24 hours; the synthesis process is simple and mild, requiring no heavy metal catalysts, thus meeting the requirements of green chemistry; it has a fast curing speed, with a curing time of ≤35 seconds under 365nm UV light; it has high hardness, reaching H-2H pencil hardness; it has a high gel content (≥94.8%), a complete cross-linking network, and excellent solvent resistance; it has significant industrial application value and market prospects in electronic packaging, metal protective coatings, and high-precision printing.

[0047] The following description is based on specific embodiments and comparative examples.

[0048] Example 1 This embodiment provides a UV-curable resin and its preparation method, including the following steps: S1. Provide raw materials, which include: 30 parts of perfluoropolyether acrylate, 15 parts of phosphate acrylate, 10 parts of pentaerythritol tetra(3-mercaptopropionate), 2 parts of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 43 parts of reactive diluent isobornyl acrylate.

[0049] S2. Preparation of prepolymer: Perfluoropolyether acrylate and phosphate hydroxyethyl acrylate are added to a reaction vessel and stirred until homogeneous. Nitrogen gas is introduced for protection, and the mixture is stirred and reacted at 70°C for 1.5 hours to obtain the prepolymer.

[0050] S3. Prepare the resin bulk. Cool the reaction system from step S1 to 50°C using a circulating water cooling system, add pentaerythritol tetra(3-mercaptopropionate), stir and mix thoroughly, and continue the reaction for 30 minutes. Monitor the reaction at 2570 cm⁻¹ using Fourier transform infrared spectroscopy. - The thiol characteristic peak at position ¹ disappears, and the resin matrix is ​​obtained.

[0051] S4. Prepare the target product by homogenizing the resin bulk with the photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone and the reactive diluent isoborneol acrylate to obtain the target UV-curable resin, which is then aged and stored in the dark.

[0052] Example 2 This embodiment provides a UV-curable resin and its preparation method, including the following steps: S1. Provide raw materials, which include: 35 parts of perfluoropolyether methacrylate, 12 parts of phosphate methacrylate, 8 parts of trimethylolpropane tris(3-mercaptopropionate), 1.5 parts of photoinitiator 1-hydroxycyclohexylphenyl ketone, and 43.5 parts of reactive diluent lauryl acrylate.

[0053] S2. Preparation of prepolymer: Perfluoropolyether methacrylate and phosphate methacrylate are added to a reaction vessel and stirred until homogeneous. Nitrogen gas is introduced for protection, and the mixture is stirred and reacted at 65°C for 2 hours to obtain the prepolymer.

[0054] S3. Prepare the resin bulk. Cool the reaction system from step S1 to 50°C using a circulating water cooling system, add trimethylolpropane tris(3-mercaptopropionate), stir and mix thoroughly, and continue the reaction for 30 minutes. Monitor the reaction at 2570 cm⁻¹ using Fourier transform infrared spectroscopy. - The thiol characteristic peak at position ¹ disappears, and the resin matrix is ​​obtained.

[0055] S4. Prepare the target product by homogenizing the resin bulk with the photoinitiator 1-hydroxycyclohexylphenyl ketone and the reactive diluent lauryl acrylate to obtain the target UV-curable resin, which is then aged and stored in the dark.

[0056] Example 3 This embodiment provides a UV-curable resin and its preparation method, including the following steps: S1. Provide raw materials, which include: 25 parts of perfluoropolyether ethyl acrylate, 18 parts of phosphate acrylate hydroxyethyl acrylate, 12 parts of pentaerythritol tetra(3-mercaptopropionate), 2.5 parts of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 42.5 parts of reactive diluent isobornyl acrylate.

[0057] S2. To prepare the prepolymer, perfluoropolyether ethyl acrylate and phosphate hydroxyethyl acrylate are added to a reaction vessel and stirred until homogeneous. Nitrogen gas is introduced for protection, and the mixture is stirred and reacted at 75°C for 2 hours to obtain the prepolymer.

[0058] S3. Prepare the resin bulk. Cool the reaction system from step S1 to 50°C using a circulating water cooling system, add pentaerythritol tetra(3-mercaptopropionate), stir and mix thoroughly, and continue the reaction for 30 minutes. Monitor the reaction at 2570 cm⁻¹ using Fourier transform infrared spectroscopy. - The thiol characteristic peak at position ¹ disappears, and the resin matrix is ​​obtained.

[0059] S4. Prepare the target product by homogenizing the resin bulk with the photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone and the reactive diluent isoborneol acrylate to obtain the target UV-curable resin, which is then aged and stored in the dark.

[0060] Example 4 This embodiment provides a UV-curable resin and its preparation method, including the following steps: S1. Provide raw materials, which include: 38 parts of perfluoropolyether methacrylate, 16 parts of phosphate hydroxyethyl acrylate, 9 parts of trimethylolpropane tris(3-mercaptopropionate), 2.2 parts of photoinitiator 1-hydroxycyclohexylphenyl ketone, and 34.8 parts of reactive diluent hydroxyethyl acrylate.

[0061] S2. Preparation of prepolymer: Perfluoropolyether methacrylate and phosphate hydroxyethyl acrylate are added to a reactor equipped with a mechanical stirrer and a temperature control system. Argon gas is continuously introduced as a protective gas to eliminate oxygen interference in the system. The reaction is carried out at a constant temperature of 75±2℃ and stirred at 250 rpm for 1 hour to obtain the prepolymer.

[0062] S3. Prepare the resin bulk. Cool the reaction system from step S1 to 55±1℃ using a circulating water cooling system. Slowly add trimethylolpropane tris(3-mercaptopropionate), controlling the addition rate to avoid drastic temperature fluctuations. Maintain the reaction temperature at 55℃ and continue stirring for 45 minutes. Monitor the reaction in real time at 2570 cm⁻¹ using a Fourier transform infrared spectroscopy instrument. -The characteristic peak at ¹ is observed until its intensity completely disappears, thus obtaining the resin matrix.

[0063] S4. To prepare the target product, the resin bulk, photoinitiator 1-hydroxycyclohexylphenyl ketone, and reactive diluent hydroxyethyl acrylate are homogenized at 500 rpm for 20 minutes to obtain UV-curable resin. The resin is then transferred to a brown light-proof container and aged at 25°C for 24 hours.

[0064] Example 5 This embodiment provides a UV-curable resin and its preparation method, including the following steps: S1. Provide raw materials, which include: 22 parts of perfluoropolyether ethyl acrylate, 19 parts of phosphate methacrylate, 14 parts of pentaerythritol tetra(3-mercaptopropionate), 1.8 parts of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 43.2 parts of reactive diluent isobornyl acrylate.

[0065] S2. Preparation of prepolymer: Perfluoropolyether ethyl acrylate and phosphate methacrylate are added sequentially to a 500 mL three-necked reactor equipped with a reflux condenser. High-purity nitrogen gas (purity ≥99.999%) is continuously introduced at a flow rate of 50 mL / min. The reaction temperature is controlled at 68±1℃ using a constant temperature water bath, and the mechanical stirring speed is set to 250 rpm. The prepolymerization reaction is maintained under these conditions for 1.8 hours to obtain the prepolymer.

[0066] S3. Prepare the resin bulk. Turn on the circulating cooling system and cool the system from step S1 to 52°C at a rate of 2°C / min. Slowly add pentaerythritol tetra(3-mercaptopropionate) dropwise using a constant pressure dropping funnel, controlling the dropping rate at 1-2 mL / min. Maintain the reaction temperature at 52±1°C, with the system temperature fluctuation not exceeding ±2°C. Continue the reaction for 50 minutes, keeping the mixture stirred steadily. Monitor the reaction progress using infrared spectroscopy to ensure that the thiol characteristic peaks completely disappear, and obtain the resin bulk.

[0067] S4. To prepare the target product, the photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone and the reactive diluent isoborneol acrylate were added to the resin body in batches and dispersed with an ultrasonic disperser at a frequency of 40 kHz for 15 minutes to obtain the UV-curable resin. The resin was then aged in a constant temperature and light-protected environment of 25±1℃ for 24 hours.

[0068] Example 6 This embodiment provides a UV-curable resin and its preparation method, including the following steps: S1. Provide raw materials, which include: 40 parts of perfluoropolyether acrylate, 20 parts of phosphate acrylate hydroxyethyl acrylate, 15 parts of pentaerythritol tetra(3-mercaptopropionate), 3 parts of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 22 parts of reactive diluent isobornyl acrylate.

[0069] S2. Prepolymer preparation: Perfluoropolyether acrylate and phosphate hydroxyethyl acrylate are added sequentially to a three-necked reactor equipped with a reflux condenser. The mixture is stirred and mixed thoroughly. High-purity nitrogen is continuously introduced. A gradient heating strategy is adopted: prepolymerization at 60℃ for 1 hour and prepolymerization at 70℃ for 1 hour to obtain the prepolymer.

[0070] S3. Prepare the resin body, turn on the circulating cooling system, cool the system in step S1 to 50°C, add pentaerythritol tetra(3-mercaptopropionate), and continue the reaction for 1 hour while maintaining stable stirring. Monitor the reaction progress by infrared spectroscopy to ensure that the thiol characteristic peaks completely disappear, and obtain the resin body.

[0071] S4. Prepare the target product by mixing the resin bulk with the photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone and the reactive diluent isoborneol acrylate to obtain the target UV-curable resin, which is then aged and stored in the dark.

[0072] Performance testing Table 1 below shows the UV-curable resin performance test results of the resins obtained in Examples 1-6 of this application.

[0073] Table 1

[0074] As can be seen from the table above, the UV-curable resin of this embodiment possesses both high adhesion and excellent acid and alkali resistance, exhibiting significant industrial application value and market prospects. Specifically, Example 4, by increasing the proportion of fluorinated monomers (38 parts) and using hydroxyethyl acrylate diluent, significantly improves hydrophobic properties (contact angle 112°), making it particularly suitable for protective coatings in electronic packaging and marine engineering equipment under high humidity environments. Example 5 uses a high proportion of phosphate monomers (19 parts) and a thiol crosslinking agent (14 parts) to form a dense crosslinked network, increasing adhesion to stainless steel substrates to 8.5 MPa (measured value), suitable for oil-resistant coatings in automotive engine compartments. Example 6 features an extreme formulation design, using the upper limit ratio for all components, achieving a gel content of 97.5% and a contact angle of 115°, suitable for long-term protection in extremely corrosive environments (such as pH values ​​1-13). All examples are based on click chemistry principles, completing key reactions in a low-temperature range of 50-55°C, reducing side reactions, and ensuring the structural regularity and performance consistency of the products.

[0075] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A method for preparing a UV-curable resin, characterized in that, Includes the following steps: The raw materials provided include: perfluoropolyether derivatives containing acrylate functional groups, phosphate functional monomers, multifunctional thiol crosslinking agents, photoinitiators, and reactive diluents; The perfluoropolyether derivative containing acrylate functional groups is subjected to a prepolymerization reaction with the phosphate functional monomer at 60-80°C to obtain a prepolymer. The prepolymer and the multifunctional thiol crosslinking agent are subjected to a click chemical reaction at 50-55°C to obtain the resin matrix. The resin bulk is mixed with the photoinitiator and the reactive diluent to obtain a UV-curable resin.

2. The preparation method according to claim 1, characterized in that, Based on the total mass of the raw materials as 100%, the perfluoropolyether derivatives containing acrylate functional groups account for 20-40% of the total mass of the raw materials; And / or, the phosphate ester functional monomer accounts for 10-20% of the total mass of the raw material; And / or, the multifunctional thiol crosslinking agent accounts for 5-15% of the total mass of the raw materials; And / or, the photoinitiator accounts for 1-3% of the total mass of the raw materials.

3. The preparation method according to claim 1 or 2, characterized in that, The perfluoropolyether derivatives containing acrylate functional groups include at least one of perfluoropolyether acrylate, perfluoropolyether methacrylate, and perfluoropolyether ethyl acrylate.

4. The preparation method according to claim 1 or 2, characterized in that, The prepolymerization reaction is carried out in an anaerobic environment; and / or the prepolymerization reaction takes 1-2 hours.

5. The preparation method according to claim 1 or 2, characterized in that, The phosphate ester functional monomer includes at least one of hydroxyethyl phosphate ester and methacrylate phosphate ester; And / or, the multifunctional thiol crosslinking agent includes at least one of pentaerythritol tetra(3-mercaptopropionate) and trimethylolpropane tri(3-mercaptopropionate).

6. The preparation method according to claim 1 or 2, characterized in that, The photoinitiator includes at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone and 1-hydroxycyclohexylphenyl ketone; And / or, the reactive diluent includes at least one of isoborneol acrylate, lauryl acrylate, and hydroxyethyl acrylate.

7. A UV-curable resin, characterized in that, The raw materials for preparing the ultraviolet-curable resin include the following components in parts by weight: Perfluoropolyether derivatives containing acrylate functional groups: 20-40 parts; Phosphate ester functional monomers: 10-20 parts; Multifunctional thiol crosslinking agent: 5-15 parts; Photoinitiator: 1-3 parts; Reactive diluent: Used to bring the total mass fraction of raw materials to 100 parts.

8. The UV-curable resin according to claim 7, characterized in that, The perfluoropolyether derivatives containing acrylate functional groups include at least one of perfluoropolyether acrylate, perfluoropolyether methacrylate, and perfluoropolyether ethyl acrylate. And / or, the phosphate ester functional monomer includes at least one of hydroxyethyl phosphate ester and methacrylate phosphate ester; And / or, the multifunctional thiol crosslinking agent includes at least one of pentaerythritol tetra(3-mercaptopropionate) and trimethylolpropane tri(3-mercaptopropionate); And / or, the photoinitiator includes at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone and 1-hydroxycyclohexylphenyl ketone; And / or, the reactive diluent includes at least one of isoborneol acrylate, lauryl acrylate, and hydroxyethyl acrylate.

9. The UV-curable resin according to claim 7 or 8, characterized in that, The ultraviolet-curable resin is prepared by the preparation method according to any one of claims 1-6.

10. An application of at least one of the ultraviolet curable resins prepared by the preparation method according to any one of claims 1-6 or the ultraviolet curable resins according to any one of claims 7-9 in the fields of electronic packaging, metal protection and high-precision printing.

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