A polyetheramine methacrylate resin, its preparation method and use

Abstract

The application discloses a polyether amine methacrylate resin and a preparation method thereof, and belongs to the field of high polymer materials. GMA (glycidyl methacrylate) and a polymerization inhibitor 4-methoxyphenol are added into a reaction bottle, under mechanical stirring and temperature rising to a certain temperature, polyether amine is added dropwise in a certain time, after dropwise addition is completed, the stirring reaction is continuously carried out at a certain temperature, and a polyether amine acrylate resin is obtained. The main chain of the polyether amine methacrylate resin is polyether, and the terminal is a methacrylate group; after UV curing, the coating layer not only has high gloss and transparency, but also has good tensile strength, hardness and wear resistance. The coating material prepared by the polyether amine methacrylate resin has high elongation at break; when the coating material is stretched by external force, it can be extended and deformed without breaking, which provides better elastic protection for electronic components.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials, and more specifically, relates to a polyetheramine methacrylate resin and its preparation method. Background Technology

[0002] In recent years, methacrylate coatings have been widely used in various fields due to their excellent properties, such as good weather resistance, chemical resistance, strong adhesion, high gloss, and rapid curing. These include, but are not limited to, the automotive, aerospace, building materials, furniture, medical devices, and optical materials industries. Especially in the industrial coatings sector, methacrylate coatings have become an indispensable part. Furthermore, methacrylate resins can also be used in the preparation of water-based coatings, offering environmentally friendly performance and meeting the modern society's demand for environmentally friendly products. Introducing polyether segments into methacrylate resin coatings is an important direction in current coating technology development, aiming to combine the excellent flexibility, hydrolytic stability, and low-temperature flexibility of polyethers with the superior weather resistance, mechanical strength, and rapid curing performance of methacrylates. With advancements in materials science and the growing market demand for high-performance, environmentally friendly coatings, the development prospects of polyether methacrylate resin coatings are extremely broad, and they are expected to occupy an even more important position in the future coatings market.

[0003] Ultraviolet (UV) curing technology refers to a technology where, under ultraviolet light irradiation, photoinitiators generate free radicals or cations, initiating reactions in photosensitive substances such as organic monomers or polymer resins in the system to polymerize and form cured or cross-linked products. Compared with traditional technologies, UV curing technology has received widespread attention due to its advantages such as fast curing speed, high energy efficiency, and low pollution. Among these, UV-curable coatings have developed rapidly in the application of photocuring technology and are highly favored by the market. UV-curable coatings are mainly composed of monomers or prepolymers, reactive diluents, photoinitiators, and catalysts. Among these, monomers or prepolymers are the most important components in the UV curing system, and their structure determines the curing speed and various physicochemical properties of the cured products.

[0004] For example, CN117143500A discloses a UV-curable electronic protective coating, its preparation method, and its application; CN112142944A discloses a low-energy UV-curable polyurethane acrylate prepolymer, its preparation method, and a UV-curable coating; CN115368535A discloses a UV / moisture dual-curing composition, its preparation method, and its application; and CN110644250A discloses a UV-curable coating adhesive for textile fabrics based on polyurethane acrylate, its preparation method, and its application. Polyurethane acrylates generally have high viscosity, slow curing speed, and high manufacturing costs. Furthermore, the reaction between water and isocyanate groups must be strictly prevented during synthesis. The reaction is prone to gelation in high humidity, requiring demanding operation. Organotin catalysts are needed in the reaction, but elemental tin is restricted by environmental regulations. Due to oxygen inhibition, the cured film of polyurethane acrylate often exhibits poor surface drying and is prone to fingerprints. Oxygen inhibition on the surface of polyester acrylates is also significant. CN112266477 discloses a UV-curable polyetheramine acrylic resin and its manufacturing method. The synthesis method involves introducing acrylate into polyetheramine and diacrylate via Michael addition. Michael addition is usually carried out under alkaline conditions. In particular, acid-sensitive functional groups (such as esters, amides, certain halogenated hydrocarbons, alcohols, etc.) may undergo side reactions (such as hydrolysis, dehalogenation, elimination, etc.) or degradation, affecting the yield.

[0005] Therefore, developing UV-curable coatings with better curing effects, the ability to quickly achieve complete curing of both the surface and interior, and good mechanical properties remains a challenge, but it has significant practical value and application prospects. Summary of the Invention

[0006] This invention relates to a polyetheramine methacrylate resin, its preparation method, and its applications. The polyetheramine methacrylate resin has a polyether backbone and methacrylate groups at the ends. After UV curing, the resulting coating not only exhibits high gloss and transparency but also good tensile strength, hardness, and abrasion resistance. Because this polyetheramine methacrylate resin has a polyether backbone and methacrylate groups at the ends, it can be UV-cured or free-radical cured, and can be used in protective coatings or etching materials.

[0007] To solve the technical problem of this invention, the proposed technical solution is: a polyetheramine methacrylate resin, the structure of which is as follows:

[0008]

[0009] In the formula, R is a polyethylene glycol ether, polypropylene glycol ether, polytetrahydrofuran ether, or a copolymer of monomers of different proportions thereof.

[0010] To solve the technical problem of this invention, another technical solution is proposed: the reaction route is as follows:

[0011]

[0012] Glycidyl methacrylate (GMA) and polymerization inhibitor 4-methoxyphenol were added to a reaction flask. The mixture was stirred mechanically and heated to a certain temperature. Polyetheramine was added dropwise over a certain time. After the addition was complete, the mixture was stirred and reacted at a certain temperature to obtain polyetheramine acrylate resin.

[0013] Preferably, the polyetheramine methacrylate resin is obtained by reacting polyetheramine with glycidyl methacrylate.

[0014] Preferably, the polyetheramine is a polymer monomer with a polyether structure as the main chain and an amino group as the terminal active functional group, wherein the polyether structure is polyethylene glycol ether, polypropylene glycol ether, polytetrahydrofuran ether, or a copolymer polyether thereof, and the average molecular weight of the polyether is in the range of 230-5000.

[0015] Preferably, the preparation process of polyetheramine methacrylate resin is as follows: glycidyl methacrylate, catalyst and polymerization inhibitor are added to a reaction flask, and the mixture is heated to a certain temperature under mechanical stirring. Polyetheramine is added dropwise over a certain time. After the addition is completed, the mixture is stirred and reacted at a certain temperature to obtain polyetheramine methacrylate resin.

[0016] The molar ratio of the reactant polyetheramine to GMA is 1:3.8–4.5;

[0017] The polymerization inhibitor is 4-methoxyphenol or other common antioxidants or polymerization inhibitors; the amount added is 10-1000 ppm by mass of the reactants.

[0018] The catalyst is triphenylphosphine or 2,4,6-tris(dimethylaminomethyl)phenol, and its addition amount is 0-1% of the reactant mass;

[0019] The reaction conditions are: reaction temperature range of 60-100℃, and reaction time of 3-10h.

[0020] Preferably, the molar ratio of reactant polyetheramine to GMA is 1:4.2-4.4; the reaction conditions are: reaction temperature of 70-80℃ and reaction time of 5-8h.

[0021] Preferably, 4.69 parts by weight of glycidyl methacrylate and 0.04 parts by weight of polymerization inhibitor 4-methoxyphenol are added to a 100ml three-necked flask, and stirred at 60°C and 200RPM for 5 minutes. Then, 15.3 parts by weight of DTHF-2300 are added within 25 minutes, and the temperature is raised to 80°C and reacted for 7 hours.

[0022] To solve the technical problem of the present invention, another technical solution is proposed: the application of the polyetheramine methacrylate resin, which is used in protective coatings or etching materials.

[0023] Preferably, the main chain of the polyetheramine methacrylate resin is polyether, and the end is methacrylate group. After UV curing, the coating formed not only has high gloss and transparency, but also good tensile strength, hardness and wear resistance.

[0024] Preferably, the obtained polyetheramine methacrylate resin is compounded with other monomers to obtain a UV-curable composition; specifically, polyetheramine methacrylate resin, isobornyl acrylate, 3-hydroxy-1-adamantyl methacrylate, and 2,4,6-trimethylbenzoyl diphenoxyphosphorus are added to a beaker, stirred and ultrasonically dispersed until the powdered solid is completely dissolved, and then poured evenly into a tetrafluoroethylene mold to make it flow smoothly and with a uniform thickness.

[0025] This UV-curable resin is obtained by reacting polyetheramine (PEA) with glycidyl methacrylate.

[0026] One of the main raw materials used is PEA, a type of polymer whose main chain is a polyether structure and whose terminal is an amino group. By selecting different polyoxyalkylene oxide structures (such as polyethylene glycol ether, polypropylene glycol ether, polytetrahydrofuran ether, and mixed polyethers), the viscosity, hydrophilicity, and mechanical properties of the polymer can be adjusted. The amino groups in PEA provide polyether amines with the possibility of reacting with a variety of compounds. For example, amino groups can react rapidly with epoxy groups. Therefore, PEA is a good curing agent for epoxy resins and can improve the toughness of the cured product.

[0027] PEA molecular chains are polymerized from various copolymers, including but not limited to polyethylene glycol, polypropylene glycol, ethylene glycol / propylene glycol copolymers, and polytetrahydrofuran. Different polyether segments typically exhibit different characteristics; for example, molecules containing polyether segments differ in hydrophilicity / hydrophobicity, mechanical strength, and elongation at break. Under the same conditions, polyethylene glycol ether exhibits the best hydrophilicity, polypropylene glycol ether the best elasticity of the cured product, and polytetrahydrofuran ether the best mechanical strength of the cured product.

[0028] This invention introduces a methacrylate double bond by reacting the terminal amine group of PEA with the epoxy group in glycidyl methacrylate (GMA). The resulting adduct has four methacrylate groups in its molecular chain, and the product can be UV-cured or peroxide-cured. The curing properties of the final product can be adjusted by modifying the structure and molecular weight of the polyetheramine segment. Furthermore, the properties of the UV-cured product can be adjusted or optimized by adding diluents and functional monomers, demonstrating broad application prospects.

[0029] The resin synthesis process referred to in this invention includes the following reaction steps:

[0030] GMA, catalyst, antioxidant, etc. are added to a reaction flask, and the mixture is heated to a certain temperature under mechanical stirring. Polyetheramine is added dropwise over a certain period of time. After the addition is complete, the reaction is continued to be stirred at a certain temperature to obtain polyetheramine acrylate resin.

[0031] Polyetheramines are polyoxypropylene ethers, polytetrahydrofuran ethers, and polyoxyethylene propylene oxide coethers with different molecular weights and functionalities, including but not limited to: polypropylene glycol ether diamines, such as DP-230 (terminated polyoxypropylene ether, molecular weight ~230), DP-2000 (terminated polyoxypropylene ether, molecular weight ~2000), TP-5000 (terminated glycerol ring-opening polypropylene glycol ether, molecular weight ~5000); polyethylene glycol polypropylene glycol coether diamines, such as DEP-600 (terminated polyoxyethylene propylene oxide coether, EO / PO = 1 / 9, molecular weight ~600); and polytetrahydrofuran ether diamines, such as DTHF-932 (terminated polytetrahydrofuran ether, molecular weight ~932), DTHF-2300 (terminated polytetrahydrofuran ether, molecular weight ~2300).

[0032] Other polyetheramines with terminal amine groups and similar structures can also be used.

[0033] Antioxidant: 4-methoxyphenol or other common antioxidants or polymerization inhibitors; the amount added is usually 10-1000 ppm by mass of the reactants.

[0034] Catalysts: triphenylphosphine and 2,4,6-tris(dimethylaminomethyl)phenol, added at 0-1% of the reactants.

[0035] The molar ratio of the reactant polyetheramine to GMA is between 1:3.8 and 4.5, preferably between 1:4.2 and 4.4.

[0036] The reaction conditions are as follows: the reaction temperature range is 60-100℃, and the reaction time is 3-10h; the preferred reaction temperature is 70-80℃, and the reaction time is 6-8h.

[0037] All reagents used in the embodiments of this invention were commercially available. Among them: 4-methoxyphenol, GMA, DP-230, DEP-600 (EO / PO=1 / 9) DP-2000, and isobornyl acrylate (IBOA) were produced by Mairui Chemical Technology Co., Ltd.; DTHF-932, DTHF-2300, and TP-5000 were produced by Yangzhou Chenhua New Material Co., Ltd.; 2-hydroxy-2-methyl-1-phenylpropanone (UV-1173) and 1,4-butanediol diacrylate (BDDA) were produced by Biye Pharmaceutical Technology Co., Ltd.; 2,4,6-trimethylbenzoyl diphenyloxyphosphine (TPO) was produced by Yuanye Biotechnology Co., Ltd.; 3-hydroxy-1-adamantyl methacrylate (HAMA) and dicyclopentyl acrylate (DCA) were produced by Shanghai Titan Technology Co., Ltd.; and 2,4,6-tris(dimethylaminomethyl)phenol was produced by Aladdin Biotechnology Co., Ltd.

[0038] Beneficial effects:

[0039] (1) The polyetheramine methacrylic acid resin adduct of the present invention introduces the ether bond-COC- segment with low cohesive energy and easy rotation into the resin backbone. It has neither the strong hydrogen bonding force of polyurethane acrylate urethane bond nor the bisphenol A structure of epoxy resin, so the resin has a lower viscosity; the tertiary amine can effectively eliminate oxygen inhibition, so the resin has better curing performance than polyurethane acrylate.

[0040] (2) Compared with the preparation method by Michael addition reaction, the ring-opening reaction of amine and epoxy group is a more controllable, highly selective and mild synthetic strategy. The reaction can be carried out completely, which is especially suitable for preparing compounds with specific structural requirements for UV curing. However, in the reaction of amine and double bond addition, especially when the double bond exists in a complex molecular structure, side reactions are prone to occur, or the reaction is incomplete due to steric hindrance.

[0041] (3) The polyetheramine methacrylic resin coating and composite material obtained by the epoxy-amine reaction of the present invention have excellent corrosion resistance and protective properties, and are widely used in anti-corrosion coatings, electronic packaging and building materials, etc.

[0042] (4) The coating material prepared by the polyetheramine methacrylic resin of the present invention has a high elongation at break. When the coating material is subjected to external tensile force, it can extend and deform without breaking, which provides better elastic protection for electronic components. When the equipment is subjected to physical deformation (such as bending, vibration or slight impact), the coating can effectively follow the deformation of the substrate without being damaged, thereby maintaining its protective function and extending the service life of electronic products.

[0043] (5) The test results show that when s-4:IBOA:HAMA:DCA:TPO is used in a mass ratio of 8:4:2.7:6:1, i.e. Example 12, and when s-4:IBOA:HAMA:TPO is used in a mass ratio of 3:2:1:0.3, i.e. Example 9, the obtained samples have both high tensile strength and greater elongation at break. The coating with both high tensile strength and suitable elongation at break not only strengthens the protection of the substrate and improves the reliability and service life of the product, but also broadens its application range in complex environments and dynamic conditions. It is an indispensable characteristic for achieving high-performance material surface treatment. Attached Figure Description

[0044] Figure 1 The FTIR spectrum of DPE-600 (EO / PO = 1 / 9) used in Example 2; the FTIR spectrum of the polyetheramine methacrylate resin obtained in Example 2.

[0045] Figure 2 The product obtained in Example 2 is a polyetheramine methacrylate resin. 1 H-NMR spectrum

[0046] Figure 3 The FTIR spectrum is obtained from the DTHF-2300 used in Example 4; the FTIR spectrum is obtained from the polyetheramine methacrylate resin product obtained in Example 4.

[0047] Figure 4 The product obtained in Example 5 is a polyetheramine methacrylate resin. 1 H-NMR spectrum

[0048] Figure 5 This is a preparation route diagram for polyetheramine methacrylate resin. Detailed Implementation

[0049] The present invention will be further illustrated below with reference to the embodiments, through which the technical solutions in the embodiments are clearly and completely described. The described embodiments are only a part of the embodiments of the present invention and do not constitute a limitation on the other claims of the present invention.

[0050] Example 1

[0051] Add 13.95 parts by weight of glycidyl methacrylate and 0.035 parts by weight of polymerization inhibitor 4-methoxyphenol to a 100 ml three-necked flask. Stir for 5 min at 60 °C and 200 RPM. Then add 5 parts by weight of DP-230 over 30 min. Finally, heat to 75 °C and react for 6 h.

[0052]

[0053] Example 2

[0054] 16.35 parts by weight of glycidyl methacrylate and 0.07 parts by weight of the polymerization inhibitor 4-methoxyphenol were added to a 100 ml three-necked flask. The mixture was stirred at 60 °C and 200 RPM for 5 min. Then, 15.8 parts by weight of DPE-600 (EO / PO = 1 / 9) were added over 20 min. Finally, the temperature was raised to 70 °C and the reaction was carried out for 8 h. FTIR analysis was performed on the raw material DPE-600, and FTIR analysis was performed on the product. 1 H-NMR analysis results are shown in Figure 1 and Figure 2 .

[0055]

[0056] Example 3

[0057] 10.33 parts by weight of glycidyl methacrylate and 0.055 parts by weight of polymerization inhibitor 4-methoxyphenol were added to a 100 ml three-necked flask. The mixture was stirred at 60 °C and 200 RPM for 5 min. Then, 15.4 parts by weight of DTHF-932 were added over 25 min. Finally, the mixture was heated to 85 °C and reacted for 6 h.

[0058]

[0059] Example 4

[0060] 4.69 parts by weight of glycidyl methacrylate and 0.04 parts by weight of 4-methoxyphenol (polymerization inhibitor) were added to a 100 ml three-necked flask. The mixture was stirred at 60 °C and 200 RPM for 5 min. Then, 15.3 parts by weight of DTHF-2300 were added over 25 min, and the mixture was heated to 80 °C and reacted for 7 h. FTIR analysis was performed on the raw material DTHF-2300 and the product polyetheramine methacrylate resin. The results are shown below. Figure 3 .

[0061]

[0062] Example 5

[0063] Add 2.28 parts by weight of glycidyl methacrylate and 0.035 parts by weight of polymerization inhibitor 4-methoxyphenol to a 100 ml three-necked flask, heat in an oil bath at 60 °C, stir for 5 min at 200 RPM, then add 18.5 parts by weight of polyetheramine TP-5000 within 30 min, and heat to 70 °C to react for 7 h.

[0064] The product was treated 1 H-NMR analysis results are shown in Figure 4 .

[0065]

[0066] Example 6

[0067] Add 2.72 parts by mass of glycidyl methacrylate, 0.026 parts by mass of polymerization inhibitor 4-methoxyphenol, and 0.13 parts by mass of triphenylphosphine to a 100 ml three-necked flask. Stir for 5 min at 60 °C and 200 RPM. Then add 10.30 parts by mass of DTHF-2300 over 25 min and heat to 80 °C for 7 h.

[0068] Example 7

[0069] Add 4.43 parts by weight of glycidyl methacrylate, 0.066 parts by weight of polymerization inhibitor 4-methoxyphenol, and 0.08 parts by weight of 2,4,6-tris(dimethylaminomethyl)phenol to a 100 ml three-necked flask. Stir for 5 min at 60 °C and 200 RPM. Then add 16.20 parts by weight of DTHF-2300 over 25 min and heat to 90 °C for 7 h.

[0070] Example 8

[0071] Add 2.99 parts by weight of glycidyl methacrylate and 0.027 parts by weight of polymerization inhibitor 4-methoxyphenol to a 100 ml three-necked flask. Stir at 60 °C and 200 RPM for 5 min. Then add 10.52 parts by weight of DP-2000 over 25 min and heat to 80 °C for 7 h.

[0072] From Example 2 Figure 1 and Figure 2 A comparison of the FTIR spectra reveals that the amino groups in the polyetheramine samples are located between 3360 and 3573 cm⁻¹. -1 It exhibits a relatively obvious dual characteristic peak, which can be found at 3435 cm⁻¹ in the polyetheramine methacrylic resin generated after the amino reaction. -1 There is a distinct characteristic peak on the left and right sides, which is analyzed to be the reaction between the epoxy group and the amino group to generate a hydroxyl group, and this is further confirmed by the polyetheramine methacrylic resin. 1 H-NMR revealed that the double bonds were still present, along with a small number of epoxy groups, proving that the required resin was successfully synthesized.

[0073] Examples 9-16

[0074] The polyetheramine methacrylate resin obtained by this invention contains methacrylate groups and can be cured by ultraviolet light or peroxide. In Examples 9-16, some of the products obtained in the examples are compounded with other monomers to obtain ultraviolet-curable compositions, which are then cured by ultraviolet light, and the mechanical properties of the cured products are tested to further illustrate the application value of the products of this invention.

[0075] Examples 9-16 are UV-curable formulations. Example 9 illustrates the compounding method: 9.00g of polyetheramine methacrylate resin, 6.00g of isobornyl acrylate, 3.00g of 3-hydroxy-1-adamantyl methacrylate, and 0.90g of 2,4,6-trimethylbenzoyl diphenoxyphosphorus are added to a 50ml beaker, stirred, and ultrasonically dispersed for 8 minutes until the powdered solid is completely dissolved. The mixture is then poured evenly into a 1mm deep tetrafluoroethylene mold to ensure a smooth and uniform flow.

[0076] The amounts of each component in the compositions of Examples 9-16 are shown in Table 1. S-4 and S-5 are the polyetheramine methacrylate resins obtained in Examples 4 and 5, respectively. These resins were compounded with various monomers and mixed uniformly to obtain UV-curable compositions. Using a BFDUV-XIK230 UV curing machine from Shenzhen Bofeda Technology Co., Ltd., the protective coating was applied to a 1mm deep PTFE mold and cured under UV light at a wavelength of 365nm and a power density of 60W / cm². 2 After curing for 45 seconds, the mechanical properties of the cured film are shown in Table 1.

[0077] The mechanical properties were tested using the INSTRON 3366 from INSTRON Corporation, with a tensile rate of 20 mm / min.

[0078] Table 1: Composition ratios and cured product properties of Examples 9-16

[0079]

[0080]

[0081] The test results showed that when s-4:IBOA:HAMA:DCA:TPO was used in a mass ratio of 8:4:2.7:6:1 (Example 12), and when s-4:IBOA:HAMA:TPO was used in a mass ratio of 3:2:1:0.3 (Example 9), the resulting samples had both high tensile strength and greater elongation at break. This coating, which combines high tensile strength with suitable elongation at break, not only strengthens the protection of the substrate and improves the reliability and service life of the product, but also broadens its application range in complex environments and dynamic conditions. It is an indispensable characteristic for achieving high-performance material surface treatment.

[0082] The polyetheramine methacrylic resin prepared by this invention has low viscosity, and the coating formed not only has high gloss and transparency, but also good tensile strength, hardness and wear resistance, thus having broad application prospects.

[0083] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention. Those skilled in the art can make various changes or modifications within the scope of the claims, which do not affect the substantive content of the present invention. Unless otherwise specified, the embodiments and features in the embodiments of this application can be arbitrarily combined with each other.

Claims

1. A method for preparing a UV-curable composition, characterized in that: The specific steps are as follows: Add 6.00g of polyetheramine methacrylate resin, 3.00g of isobornyl acrylate, 2.00g of 3-hydroxy-1-adamantyl methacrylate, 4.5g of dicyclopentyl acrylate, and 0.75g of 2,4,6-trimethylbenzoyl diphenoxyphosphorus to a 50ml beaker, stir and ultrasonically disperse for 8 minutes until the powdered solid is completely dissolved, and pour it evenly into a 1 mm deep tetrafluoroethylene mold to make it flow smoothly and with a uniform thickness; The preparation method of polyetheramine methacrylic resin is as follows: 4.69 parts by weight of glycidyl methacrylate and 0.04 parts by weight of polymerization inhibitor 4-methoxyphenol were added to a 100 ml three-necked flask. The mixture was stirred at 60 °C and 200 rpm for 5 min. Then, 15.3 parts by weight of polyetheramine DTHF-2300 were added over 25 min. The mixture was heated to 80 °C and reacted for 7 h to obtain the product polyetheramine methacrylate resin.

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