Wear-resistant waterborne uv light-cured resin and preparation method thereof

Abstract

The present application relates to the technical field of resin, in particular to a wear-resistant waterborne UV photocuring resin and a preparation method thereof. The preparation method comprises the following steps: (1) mixing diisocyanate, polymeric polyol, catalyst and organic solvent in an inert gas atmosphere, and reacting at 60-90 DEG C for 1-4 h; (2) cooling to 50-70 DEG C, adding carboxylic acid chain extender and continuing to react for 1-3 h, then increasing the temperature to 80-90 DEG C, and adding hydroxyl chain extender, amine chain extender, catalyst and organic solvent and reacting for 2-4 h; reducing the temperature to 70-80 DEG C, adding polymerization inhibitor, wear-resistant ethanol solution, hydroxypropyl methacrylate and catalyst and reacting for 1-3 h to obtain a mixed solution; (3) cooling the mixed solution to 20-40 DEG C, adding triethylamine and water, stirring and emulsifying, adding hot water at 50-90 DEG C, and removing solvent under reduced pressure to obtain the wear-resistant waterborne UV photocuring resin. The resin has the advantages of waterborne environmental protection, high wear resistance, fast curing, strong adhesion and excellent flame retardant performance, and is suitable for the fields of coating and electronic packaging.

Description

Technical Field

[0001] This invention relates to the field of resin technology, specifically to a wear-resistant water-based UV-curable resin and its preparation method. Background Technology

[0002] Waterborne UV-curable resins are a new type of polymer material that combines UV curing technology with a water-based system. Their molecular structure contains both photosensitive groups (such as acrylate double bonds) and hydrophilic groups (such as carboxyl and hydroxyl groups). These resins achieve rapid curing through free radical polymerization initiated by UV light, while using water as the dispersion medium, offering the dual advantages of environmental friendliness and high-efficiency production. Currently, this material is widely used in wood coatings, automotive topcoats, electronic product packaging, 3D printing, and flexible packaging, demonstrating unique value, especially in industrial settings requiring rapid prototyping and low VOC emissions.

[0003] In recent years, waterborne UV-curable resins have shown broad application prospects in coatings, electronic packaging, and other fields due to their environmentally friendly characteristics and high-efficiency curing performance. However, several key technical defects still exist in the current market for wear-resistant waterborne UV resins. First, it is often difficult to balance the mechanical strength and wear resistance of the resin matrix. While high crosslinking density can improve hardness, it can also increase the brittleness of the material, making it prone to microcracks under dynamic loads. Second, the introduction of traditional wear-resistant fillers (such as micron-sized alumina) can improve surface hardness, but it can significantly reduce the resin's light transmittance and curing efficiency, affecting the penetration depth of UV light. However, unmodified nanoparticles are prone to agglomeration due to their high surface energy, resulting in uneven dispersion in the resin matrix. This not only fails to fully exert their reinforcing effect but may also become stress concentration points, thus reducing the material's mechanical properties. Ordinary physical blending methods are difficult to achieve strong interfacial bonding between the filler and the matrix, making interfacial delamination prone to occur under stress. Therefore, the dispersion stability problem of nanoscale wear-resistant fillers has not been fundamentally solved. Filler agglomeration not only weakens the reinforcing effect but may also become a stress concentration source, accelerating material failure.

[0004] Clearly, traditional waterborne UV resins still have significant shortcomings in terms of mechanical properties and abrasion resistance, making it difficult to meet the stringent durability requirements of high-end applications. The abrasion resistance of resins is closely related to crosslinking density, filler dispersion, and interfacial bonding strength, and existing technologies often struggle to simultaneously address these key factors. Furthermore, with increasingly stringent environmental regulations, developing resin systems that combine high performance and environmental friendliness has become an important research direction in the industry. Summary of the Invention

[0005] To address the shortcomings of the existing technology, this invention provides a wear-resistant water-based UV-curable resin and its preparation method.

[0006] To solve the above technical problems, the technical scheme adopted by the present application is:

[0007] A preparation method of the wear-resistant waterborne UV photocurable resin comprises the following steps:

[0008] (1) In an inert gas atmosphere, mix diisocyanate, polymeric polyol, catalyst and organic solvent, and react at 60-90℃ for 1-4h;

[0009] (2) Cool to 50-70℃, add carboxylic acid chain extender and continue to react for 1-3h, then raise the temperature to 80-90℃, add hydroxyl chain extender, amine chain extender, catalyst and organic solvent and react for 2-4h; finally, lower the temperature to 70-80℃, add polymerization inhibitor, wear-resistant agent ethanol solution, hydroxypropyl methacrylate and catalyst and react for 1-3h to obtain a mixed solution;

[0010] (3) Lower the mixed solution to 20-40℃, add triethylamine and water, stir and emulsify, then add hot water at 50-90℃, and remove the solvent under reduced pressure to obtain the wear-resistant waterborne UV photocurable resin.

[0011] The wear-resistant waterborne UV photocurable resin prepared by the present application has multiple excellent performances: first, diisocyanate is reacted with polymeric polyol to form a polyurethane main chain, which endows the resin with high elasticity and mechanical strength; second, hydrophilic groups are introduced by carboxylic acid chain extender, and the resin has excellent water dispersibility by neutralization into salt with triethylamine, realizing an environmentally friendly waterborne system; third, the introduction of hydroxyl chain extender and hydroxypropyl methacrylate provides high-reactivity double bonds, forming a high-crosslinking-density network during UV curing, improving the curing rate and film hardness; in addition, the wear-resistant agent has epoxy phosphorus-modified silane coupling agent modified nanoparticles with wear-resistant structure, which enhances the interfacial bonding force through the dual action of chemical bonding and physical entanglement, significantly improving the wear resistance and impact resistance; finally, the addition of the polymerization inhibitor ensures the storage stability. The resin molecule has epoxy phosphorus-modified silane coupling agent modified nanoparticles with wear-resistant structure and flexible organosilicon polyurethane segments, and has a high-water-soluble organic segment on the side chain, which has carboxylic acid, hydroxyl and amine groups that can be water-soluble at the same time. When dissolved in water, a high-water-soluble UV photocurable waterborne resin can be obtained. The resin has waterborne environmental protection, high wear resistance, fast curing, strong adhesion and excellent mechanical properties, and is suitable for high-end coatings, electronic packaging and other fields.

[0012] Preferably, the polymeric polyol in step (1) comprises any one or a combination of at least two of polycaprolactone triol, polytetrahydrofuran ether diol, polyethylene glycol, polypropylene glycol, polycaprolactone diol or polycarbonate diol;

[0013] The diisocyanate includes any one or at least two of hexamethylene diisocyanate, toluene diisocyanate, 4,4-diisocyanate dicyclohexyl methane, isophorone diisocyanate.

[0014] Preferably, the organic solvent is any one of tetrahydrofuran, cyclohexane, toluene, acetone.

[0015] Preferably, the catalyst in the step (1) or step (2) includes any one of dibutyl tin dilaurate, stannous octoate, bismuth neodecanoate, tetramethylbutanediamine.

[0016] Preferably, the carboxyl-based chain extender in the step (2) includes one or a combination of at least two of 2,2-dimethylol propionic acid, 2,2-dimethylol butyric acid.

[0017] The hydroxyl-based chain extender includes any one or a combination of at least two of hydroxyethyl acrylate, hydroxypropyl methacrylate, or hydroxypropyl acrylate.

[0018] The amine-based chain extender includes any one or a combination of at least two of ethylenediamine, propylenediamine, isophorone diamine, hydrazine hydrate, 2,4-toluene diamine, 2-methyl-1,5-pentanediamine, piperazine, or hexamethylenediamine.

[0019] Preferably, the polymerization inhibitor in the step (2) includes any one of hydroquinone, p-hydroxyanisole, p-methoxyphenol.

[0020] Inorganic nano-filler can increase the strength of the composite resin and also improve the wear resistance of the composite resin. However, direct addition of unmodified nanoparticles is prone to agglomeration, and it is difficult to disperse uniformly in the resin matrix, which leads to easy shedding of the added nanoparticles, affecting the overall performance of the resin. Through modification, the surface of the filler particles is connected with varying amounts of modifiers. The epoxy group modified silane coupling agent in the wear-resistant agent forms a chemical bond with the hydroxyl / carboxyl groups of the resin matrix through ring-opening reaction of the epoxy group, and its phosphorus modified structure endows the material with flame retardancy. At the same time, after the surface of the nanoparticles is modified by the silane coupling agent, the silicon hydroxyl groups form hydrogen bonds with the polar groups in the resin, and the carboxyl and amino groups in the grafted amino acid further form ionic or covalent bonds with the resin matrix, so there is a relatively strong network formed between the particles. During the processing, the resin molecular chains can penetrate into the network formed by the filler particles and entangle on the surface of the filler particles, thereby forming entanglement. Due to the complex entanglement of the resin molecular chains, the resin molecular chains are not easy to slip, thereby leading to a significant improvement in the mechanical properties of the resin composite material. This multi-level interfacial force makes the nanoparticles uniformly dispersed and firmly combined in the resin. In addition, the rigid skeleton of the nanoparticles and the flexible chain segments of the resin form a "rigid-flexible" composite structure. When subjected to external force, the nanoparticle network can effectively disperse stress and inhibit molecular chain slipping, thereby improving the wear resistance of the resin while maintaining excellent impact resistance and dimensional stability.

[0021] Preferably, the preparation method of the wear-resistant agent is as follows:

[0022] S1, mixing epoxy resin with organic solvent to form a dispersion, adding isocyanate silane coupling agent for reaction, then adding phosphoric acid for phosphorus modification to obtain epoxy group modified silane coupling agent;

[0023] S2, dispersing the nanoparticles in an ethanol aqueous solution, adding the epoxy group modified silane coupling agent for surface modification, and then treating with an amino acid aqueous solution to obtain the wear-resistant agent after centrifugal drying.

[0024] The reaction mechanism of the present application is as follows: S1 takes epoxy resin and isocyanate silane coupling agent as main raw materials, under the condition of heating and stirring, ring-opening addition reaction occurs between epoxy group and isocyanate group, forming urethane bond, so that the silane coupling agent is grafted onto the epoxy resin, after adding phosphoric acid, the phosphoric acid reacts with the epoxy group or the hydroxyl group, introducing phosphate group, improving the flame retardance and thermal stability of the wear-resistant agent, forming epoxy phosphorus modified silane coupling agent, giving it flame retardance and interfacial activity; S2 takes nanoparticles and epoxy phosphorus modified silane coupling agent as main reaction raw materials, under the condition of heating and stirring, the methoxy group of the epoxy phosphorus modified silane coupling agent hydrolyzes to form silanol, which condenses with the hydroxyl group on the surface of the nanoparticles, forming Si-O-Si covalent bond, realizing the surface grafting of the nanoparticles; the epoxy group on the epoxy phosphorus modified silane coupling agent and the carboxyl group of the amino acid occur ring-opening reaction under weak acidic condition, forming ester bond and hydroxyl group, so that the amino acid is grafted onto the surface of the nanoparticles, forming organic-inorganic hybrid structure, which is chemically bonded with the matrix when the resin is cured, forming three-dimensional network, synergistically enhancing the wear resistance, the phosphorus modification gives the wear-resistant agent flame retardance, while the amino and carboxyl groups of the amino acid can enhance the compatibility with the resin matrix, improving the dispersibility and interfacial bonding force.

[0025] Further, the preparation method of the wear-resistant agent is as follows:

[0026] S1, under the protection of nitrogen atmosphere, mix 7-14 parts by weight of epoxy resin and 40 parts by weight of solvent, stir at 50-80℃, 400-800rpm for 0.5-2h, to obtain an epoxy resin dispersion; then add 8-16 parts by weight of isocyanate silane coupling agent, continue to react for 1-4h; add 1-3 parts by weight of anhydrous phosphoric acid at a speed of 1-3mL / min, stir at 40-70℃, 200-600rpm for 2-6h, remove the solvent by reduced pressure distillation, to obtain epoxy phosphorus modified silane coupling agent;

[0027] S2, add 2-8 parts by weight of nanoparticles to 120-300 parts by weight of 20-40wt% ethanol aqueous solution to obtain a dispersion suspension; add 0.8-2 parts by weight of epoxy phosphorus modified silane coupling agent, adjust the pH to 6-7 with 1mol / L hydrochloric acid, stir at 50-80℃, 100-500rpm for 2-7h; then add 15-30 parts by weight of 10-20wt% amino acid aqueous solution, continue to react for 2-6h, centrifuge, wash, dry, to obtain the wear-resistant agent.

[0028] Preferably, the epoxy resin is at least one of bisphenol A type epoxy resin, polyphenol type glycidyl ether epoxy resin, hydrogenated bisphenol A type epoxy resin, and bisphenol S type epoxy resin.

[0029] Preferably, the solvent in S1 is any one of N,N-dimethylformamide, acetone, butanone, dimethyl sulfoxide.

[0030] Preferably, the nanoparticles are at least one of silicon dioxide, aluminum oxide, calcium carbonate or boron nitride, with a particle size of 20-200 nm; the amino acid is a hydroxyl or thiol-containing amino acid; further, the amino acid is at least one of glycine, serine, threonine, cysteine.

[0031] Preferably, the isocyanate-based silane coupling agent includes one or both of 3-isocyanate propyl trimethoxysilane and isocyanate propyl triethoxysilane.

[0032] Preferably, the components include, by weight:

[0033] Diisocyanate 5-10 parts;

[0034] Polymeric polyol 10-20 parts;

[0035] Carboxylic acid-based chain extender 0.5-2 parts

[0036] Hydroxyl-based chain extender 0.5-3 parts;

[0037] Amine-based chain extender 1-4 parts;

[0038] Wear-resistant agent 0.5-10 parts;

[0039] Acrylate monomer 3-10 parts;

[0040] Total amount of catalyst 0.01-0.1 parts;

[0041] Total amount of organic solvent 10-30 parts;

[0042] Water 40-100 parts.

[0043] A wear-resistant water-based UV light-cured resin is obtained by the above preparation method.

[0044] The present application has the following advantages: 1. The present application provides a wear-resistant water-based UV light-cured resin and a preparation method thereof. The present application utilizes the interaction between various substances, optimizes the component ratio and preparation process parameters, and prepares a wear-resistant water-based UV light-cured resin. The resin has strong adhesion and wear resistance, can maintain good flame retardation effect at high temperature, has long service life, and avoids cracking and falling off problems when used at high temperature for a long time.

[0045] 2, The resin prepared by the application has the epoxy group phosphorus modified silane coupling agent modified nanoparticles with wear-resistant structure, flexible organosilicon polyurethane chain segment, and high water-soluble organic chain segment with carboxylic acid, hydroxyl and amine groups which are water-soluble at the same time, which is dissolved in water to obtain a high water-soluble UV-curable water-based resin. The resin has water-based environmental protection, high wear resistance, fast curing, strong adhesion and excellent flame retardation, and is suitable for high-end coatings, electronic packaging and the like.

[0046] 3, The preparation of the application is simple, the process is feasible, the production cost is low, the environment is friendly, and the applicability is very wide. DETAILED DESCRIPTION

[0047] The above inventive content of the application will be further described in combination with specific embodiments, but this should not be understood as limiting the scope of the above subject matter of the application to the following examples.

[0048] In the application, some raw materials are introduced, and other raw materials not introduced are commercially available:

[0049] Polycaprolactone triol is purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., and the article number is P303596.

[0050] Polycarbonate diol is purchased from Jining Huipeng Chemical Co., Ltd., and the article number is 25-3-20.

[0051] Nano-silicon dioxide is purchased from Hubei Hui Fu Nanometer Material Co., Ltd., and the brand is HL-150.

[0052] Boron nitride is purchased from Qinghe County Chaotai Metal Material Co., Ltd., and the model is AM-HBN-Q-01.

[0053] Bisphenol A type epoxy resin is purchased from Jining Fangyi Chemical Co., Ltd., and the brand is E-42.

[0054] Example 1

[0055] A preparation method of a wear-resistant water-based UV light curing resin, comprising the following steps:

[0056] (1) In an inert gas atmosphere, 6 parts by weight of diisocyanate, 15 parts by weight of polymeric polyol, 0.5 parts by weight of dibutyltin dilaurate and 10 parts by weight of tetrahydrofuran are mixed uniformly and reacted at 80℃ for 2h;

[0057] (2) Cool down to 60°C, add 0.8 parts by weight of carboxylic acid chain extender and continue the reaction for 2 hours. Then raise the temperature to 85°C, add 1 part by weight of hydroxyl chain extender, 2 parts by weight of amine chain extender, 0.05 parts by weight of dibutyltin dilaurate and 4 parts by weight of tetrahydrofuran and react for 3 hours. Finally, lower the temperature to 75°C, add 0.02 parts by weight of polymerization inhibitor, 5 parts by weight of hydroxypropyl methacrylate and 0.03 parts by weight of dibutyltin dilaurate and react for 2 hours to obtain a mixed solution.

[0058] (3) Cool the above mixed solution to 30°C, add 0.8 parts by weight of triethylamine and 40 parts by weight of water, stir at 400 rpm for 45 min to obtain polyurethane acrylate prepolymer; add hot water at 80°C dropwise at 1000 rpm, continue stirring for 30 min after the addition is complete, remove solvent under reduced pressure to obtain wear-resistant waterborne UV-curable resin.

[0059] The diisocyanate is composed of isophorone diisocyanate and 4,4-diisocyanate dicyclohexylmethane in a mass ratio of 1:1.

[0060] The polymeric polyol is composed of polycaprolactone triol and polycarbonate diol in a mass ratio of 2:1.

[0061] The carboxylic acid chain extender is 2,2-dihydroxymethylpropionic acid.

[0062] The hydroxyl chain extender is hydroxyethyl acrylate.

[0063] The amine chain extender is isoflurane diamine.

[0064] The polymerization inhibitor includes hydroquinone.

[0065] Example 2

[0066] A method for preparing a wear-resistant water-based UV-curable resin includes the following steps:

[0067] (1) In an inert gas atmosphere, 6 parts by weight of diisocyanate, 15 parts by weight of polymeric polyol, 0.5 parts by weight of dibutyltin dilaurate and 10 parts by weight of tetrahydrofuran are mixed evenly and reacted at 80°C for 2 hours.

[0068] (2) Cool down to 60°C, add 0.8 parts by weight of carboxylic acid chain extender and continue the reaction for 2 hours. Then raise the temperature to 85°C, add 1 part by weight of hydroxyl chain extender, 2 parts by weight of amine chain extender, 0.05 parts by weight of dibutyltin dilaurate and 4 parts by weight of tetrahydrofuran and react for 3 hours. Finally, lower the temperature to 75°C, add 0.02 parts by weight of polymerization inhibitor, 7.5 parts by weight of ethanol solution containing 5 wt% wear-resistant agent, 5 parts by weight of hydroxypropyl methacrylate and 0.03 parts by weight of dibutyltin dilaurate and react for 2 hours to obtain a mixed solution.

[0069] (3) The above mixed solution is reduced to 30°C, 0.8 parts by weight of triethylamine and 40 parts by weight of water are added, and stirring is carried out at 400 rpm for 45 min to obtain a polyurethane acrylate prepolymer; hot water at 80°C is added dropwise at a rotation speed of 1000 rpm, and stirring is continued for 30 min after the dropwise addition is completed; solvent is removed under reduced pressure to obtain a wear-resistant water-based UV curing resin.

[0070] The diisocyanate is isophorone diisocyanate and 4,4-diisocyanate dicyclohexyl methane in a mass ratio of 1:1.

[0071] The polymeric polyol is composed of polycaprolactone triol and polycarbonate diol in a mass ratio of 2:1.

[0072] The carboxylic acid chain extender is 2,2-dimethylol propionic acid.

[0073] The hydroxyl chain extender is hydroxyethyl acrylate.

[0074] The amine chain extender is isophorone diamine.

[0075] The polymerization inhibitor includes hydroquinone.

[0076] The wear-resistant agent is nano-silicon dioxide.

[0077] Example 3

[0078] A preparation method of a wear-resistant water-based UV curing resin, comprising the following steps:

[0079] (1) In an inert gas atmosphere, 6 parts by weight of diisocyanate, 15 parts by weight of polymeric polyol, 0.5 parts by weight of dibutyltin dilaurate, and 10 parts by weight of tetrahydrofuran are mixed uniformly and reacted at 80°C for 2h;

[0080] (2) The temperature is reduced to 60°C, 0.8 parts by weight of carboxylic acid chain extender is added and reacted for 2h, then the temperature is raised to 85°C, 1 part by weight of hydroxyl chain extender, 2 parts by weight of amine chain extender, 0.05 parts by weight of dibutyltin dilaurate, and 4 parts by weight of tetrahydrofuran are added and reacted for 3h; finally, the temperature is reduced to 75°C, 0.02 parts by weight of polymerization inhibitor, 7.5 parts by weight of 5wt% wear-resistant agent ethanol solution, 5 parts by weight of hydroxypropyl methacrylate, and 0.03 parts by weight of dibutyltin dilaurate are added and reacted for 2h to obtain a mixed solution;

[0081] (3) The above mixed solution is reduced to 30℃, 0.8 parts by weight of triethylamine and 40 parts by weight of water are added, and stirring is carried out at 400 rpm for 45 min to obtain a polyurethane acrylate prepolymer; hot water at 80℃ is added dropwise at a rotation speed of 1000 rpm, and stirring is continued for 30 min after the dropwise addition is completed; solvent is removed under reduced pressure to obtain a wear-resistant water-based UV photocuring resin.

[0082] The polymeric polyol is composed of polycaprolactone triol and polycarbonate diol at a mass ratio of 2:1.

[0083] The carboxylic acid chain extender is 2,2-dimethylol propionic acid.

[0084] The hydroxyl chain extender is hydroxyethyl acrylate.

[0085] The amine chain extender is isophorone diamine.

[0086] The polymerization inhibitor includes hydroquinone.

[0087] The preparation method of the wear-resistant agent is as follows:

[0088] 5 parts by weight of nano-silicon dioxide is added to 200 parts by weight of a 30wt% ethanol aqueous solution to obtain a dispersion suspension; 1.2 parts by weight of 3-isocyanate propyl trimethoxysilane is added, and the pH is adjusted to 6.5 with 1 mol / L hydrochloric acid; stirring is carried out at 65℃ and 300 rpm for 4 h, centrifugation, washing, and drying are carried out to obtain a wear-resistant agent.

[0089] Example 4

[0090] A preparation method of a wear-resistant water-based UV photocuring resin, comprising the following steps:

[0091] (1) In an inert gas atmosphere, 6 parts by weight of diisocyanate, 15 parts by weight of polymeric polyol, 0.5 parts by weight of dibutyltin dilaurate, and 10 parts by weight of tetrahydrofuran are uniformly mixed and reacted at 80℃ for 2 h;

[0092] (2) The temperature is reduced to 60℃, 0.8 parts by weight of a carboxylic acid chain extender is added and reacted for 2 h, then the temperature is increased to 85℃, 1 part by weight of a hydroxyl chain extender, 2 parts by weight of an amine chain extender, 0.05 parts by weight of dibutyltin dilaurate, and 4 parts by weight of tetrahydrofuran are added and reacted for 3 h; finally, the temperature is reduced to 75℃, 0.02 parts by weight of a polymerization inhibitor, 7.5 parts by weight of an ethanol solution containing 5wt% of a wear-resistant agent, 5 parts by weight of hydroxypropyl methacrylate, and 0.03 parts by weight of dibutyltin dilaurate are added and reacted for 2 h to obtain a mixed solution;

[0093] (3) The mixed solution is cooled to 30℃, 0.8 parts by weight of triethylamine and 40 parts by weight of water are added, and stirring is carried out at 400 rpm for 45 min to obtain a polyurethane acrylate prepolymer; hot water at 80℃ is added dropwise at a rotation speed of 1000 rpm, and stirring is continued for 30 min after the dropwise addition is completed; and solvent is removed under reduced pressure to obtain a wear-resistant water-based UV photocuring resin.

[0094] The polymeric polyol is composed of polycaprolactone triol and polycarbonate diol at a mass ratio of 2:1.

[0095] The carboxylic acid chain extender is 2,2-dimethylol propionic acid.

[0096] The hydroxyl chain extender is hydroxyethyl acrylate.

[0097] The amine chain extender is isophorone diamine.

[0098] The polymerization inhibitor includes hydroquinone.

[0099] The preparation method of the wear-resistant agent is as follows:

[0100] S1, under a nitrogen protective atmosphere, 10 parts by weight of bisphenol A type epoxy resin and 40 parts by weight of N,N-dimethylformamide are mixed and stirred at 60℃ and 600 rpm for 1 h to obtain a bisphenol A type epoxy resin dispersion; then 12 parts by weight of 3-isocyanate propyl trimethoxysilane is added and the reaction is continued for 2 h; solvent is removed by distillation under reduced pressure to obtain an epoxy-modified silane coupling agent;

[0101] S2, 5 parts by weight of nano-silicon dioxide is added to 200 parts by weight of a 30wt% ethanol aqueous solution to obtain a dispersion suspension; 1.2 parts by weight of the epoxy-modified silane coupling agent is added, and the pH is adjusted to 6.5 with 1 mol / L hydrochloric acid, and stirring is carried out at 65℃ and 300 rpm for 4 h; centrifugation, washing and drying are carried out to obtain a wear-resistant agent.

[0102] Example 5

[0103] A preparation method of a wear-resistant water-based UV photocuring resin, comprising the following steps:

[0104] (1) In an inert gas atmosphere, 6 parts by weight of diisocyanate, 15 parts by weight of polymeric polyol, 0.5 parts by weight of dibutyltin dilaurate and 10 parts by weight of tetrahydrofuran are mixed uniformly and reacted at 80℃ for 2 h;

[0105] (2) Cool down to 60°C, add 0.8 parts by weight of carboxylic acid chain extender and continue the reaction for 2 hours. Then raise the temperature to 85°C, add 1 part by weight of hydroxyl chain extender, 2 parts by weight of amine chain extender, 0.05 parts by weight of dibutyltin dilaurate and 4 parts by weight of tetrahydrofuran and react for 3 hours. Finally, lower the temperature to 75°C, add 0.02 parts by weight of polymerization inhibitor, 7.5 parts by weight of ethanol solution containing 5 wt% wear-resistant agent, 5 parts by weight of hydroxypropyl methacrylate and 0.03 parts by weight of dibutyltin dilaurate and react for 2 hours to obtain a mixed solution.

[0106] (3) Cool the above mixed solution to 30°C, add 0.8 parts by weight of triethylamine and 40 parts by weight of water, stir at 400 rpm for 45 min to obtain polyurethane acrylate prepolymer; add hot water at 80°C dropwise at 1000 rpm, continue stirring for 30 min after the addition is complete, remove solvent under reduced pressure to obtain wear-resistant waterborne UV-curable resin.

[0107] The polymeric polyol is composed of polycaprolactone triol and polycarbonate diol in a mass ratio of 2:1.

[0108] The carboxylic acid chain extender is 2,2-dihydroxymethylpropionic acid.

[0109] The hydroxyl chain extender is hydroxyethyl acrylate.

[0110] The amine chain extender is isoflurane diamine.

[0111] The polymerization inhibitor includes hydroquinone.

[0112] The method for preparing the wear-resistant agent is as follows:

[0113] S1. Under a nitrogen protective atmosphere, 10 parts by weight of bisphenol A epoxy resin and 40 parts by weight of N,N-dimethylformamide were mixed and stirred at 60°C and 600 rpm for 1 h to obtain a bisphenol A epoxy resin dispersion; then 12 parts by weight of 3-isocyanate-propyltrimethoxysilane were added and the reaction was continued for 2 h; 1.5 parts by weight of anhydrous phosphoric acid were added dropwise at a rate of 2 mL / min and stirred at 50°C and 400 rpm for 3 h; the solvent was removed by vacuum distillation to obtain an epoxy-phosphorus modified silane coupling agent;

[0114] S2. Add 5 parts by weight of nano-silica to 200 parts by weight of 30wt% ethanol aqueous solution and ultrasonically disperse to obtain a dispersion suspension; add 1.2 parts by weight of epoxy phosphorus modified silane coupling agent, adjust the pH to 6.5 with 1mol / L hydrochloric acid, and stir at 65℃ and 300rpm for 4h; centrifuge, wash, and dry to obtain wear-resistant agent.

[0115] Example 6

[0116] A preparation method of a wear-resistant waterborne UV photocuring resin, comprising the following steps:

[0117] (1) In an inert gas atmosphere, 6 parts by weight of diisocyanate, 15 parts by weight of polymeric polyol, 0.5 parts by weight of dibutyltin dilaurate and 10 parts by weight of tetrahydrofuran are uniformly mixed and reacted at 80℃ for 2h;

[0118] (2) The temperature is lowered to 60℃, 0.8 parts by weight of carboxylic acid chain extender is added and reacted for 2h, then the temperature is raised to 85℃, 1 part by weight of hydroxyl chain extender, 2 parts by weight of amine chain extender, 0.05 parts by weight of dibutyltin dilaurate and 4 parts by weight of tetrahydrofuran are added and reacted for 3h; finally, the temperature is lowered to 75℃, 0.02 parts by weight of polymerization inhibitor, 7.5 parts by weight of 5wt% wear-resistant agent ethanol solution, 5 parts by weight of hydroxypropyl methacrylate and 0.03 parts by weight of dibutyltin dilaurate are added and reacted for 2h to obtain a mixed solution;

[0119] (3) The above mixed solution is lowered to 30℃, 0.8 parts by weight of triethylamine and 40 parts by weight of water are added, stirred at 400rpm for 45min to obtain a polyurethane acrylate prepolymer; hot water at 80℃ is added dropwise at a speed of 1000rpm, after the dropwise addition is completed, the stirring is continued for 30min, and the solvent is removed under reduced pressure to obtain a wear-resistant waterborne UV photocuring resin.

[0120] The polymeric polyol is composed of polycaprolactone triol and polycarbonate diol according to a mass ratio of 2:1.

[0121] The carboxylic acid chain extender is 2,2-dimethylol propionic acid.

[0122] The hydroxyl chain extender is hydroxyethyl acrylate.

[0123] The amine chain extender is isophorone diamine.

[0124] The polymerization inhibitor includes hydroquinone.

[0125] The preparation method of the wear-resistant agent is as follows:

[0126] S1, under the protection of nitrogen atmosphere, 10 parts by weight of bisphenol A type epoxy resin and 40 parts by weight of N,N-dimethylformamide are mixed and stirred at 60℃ and 600rpm for 1h to obtain a bisphenol A type epoxy resin dispersion; 12 parts by weight of 3-isocyanate propyl trimethoxysilane is added and reacted for 2h; 1.5 parts by weight of anhydrous phosphoric acid is added dropwise at a speed of 2mL / min, stirred at 50℃ and 400rpm for 3h, and the solvent is removed by distillation under reduced pressure to obtain an epoxy group phosphorus modified silane coupling agent;

[0127] S2, 5 parts by weight of nano-silica was added to 200 parts by weight of 30 wt% ethanol aqueous solution and ultrasonically dispersed to obtain a dispersion suspension; 1.2 parts by weight of epoxy group phosphorus modified silane coupling agent was added, and the pH was adjusted to 6.5 with 1 mol / L hydrochloric acid, and stirred at 65°C and 300 rpm for 4h; then 20 parts by weight of 15 wt% amino acid aqueous solution was added, and the reaction was continued for 3h, centrifuged, washed, and dried to obtain the wear-resistant agent.

[0128] The amino acid is serine.

[0129] Example 7

[0130] The same as Example 6, except that the nanoparticles in the wear-resistant agent are boron nitride.

[0131] Example 8

[0132] The same as Example 6, except that the nanoparticles in the wear-resistant agent are boron nitride.

[0133] Test Example 1

[0134] The wear-resistant water-based UV photocuring resin prepared in the above Examples 1-8 was configured into a coating for testing, and the coating was prepared as follows: 30 parts by weight of the wear-resistant water-based UV photocuring resin prepared in the above Examples 1-8, 12 parts by weight of the active diluent isobornyl acrylate, 3 parts by weight of the photoinitiator 1-hydroxycyclohexyl phenyl ketone, and 55 parts by weight of water were stirred to obtain a wear-resistant water-based UV photocuring resin coating. The above wear-resistant water-based UV photocuring resin coating was applied to a test panel with an applicator, and then irradiated with a UV lamp for 30 seconds to obtain a photocured film. The UV lamp light source was a 365 nm wavelength UV-LED point light source.

[0135] 1. Adhesion test: The fiber-reinforced cement board surface specified in the national standard GB / T 9271-2008 "Standard Test Panel for Color Paint and Varnish" was coated with the wear-resistant water-based UV photocuring resin coating obtained in each of the above examples, and a paint film with a thickness of 250 μm was obtained after adjusting at 25°C and a relative humidity of 50% for 24h. The test panel was used for the following tests. The adhesion test was carried out according to the national standard GB / T9286-2021 "Color Paint and Varnish Grating Test", the cutting interval was 1mm, the adhesive tape tearing time was 1.0s, and 5 groups of test samples were tested for each group. The test results are shown in Table 1.

[0136] Abrasion resistance test: the test plate obtained above was tested by using the national standard GB / T 1768-2006 "Determination of abrasion resistance of paint and varnish - rotating rubber wheel method", under the conditions of temperature 25℃, relative humidity 50%, the rotating speed of the abrasion tester was 60r / min, the test time was 3min, the mass loss of abrasion = the initial test plate mass - the test plate mass after the test. Each group of samples was tested for 5 groups, and the average value was taken, and the test results are shown in Table 1.

[0137] Table 1 adhesion and abrasion resistance test results

[0138]

[0139]

[0140] 2, flame retardant performance test: the abrasion-resistant water-based UV light-cured resin coating was coated on the experimental plate to form a film layer with a thickness of about 2mm, dried and formed at room temperature, and a temperature probe was connected to the back of the experimental plate; after the coating layer was formed and cured, a high-temperature spray gun with a temperature of 1000℃ was used to directly heat the coating layer for 180s, and the change of the coating layer was observed during the process, and the results are shown in Table 2.

[0141] Table 2 flame retardant performance test results

[0142] Film layer changes Example 1 Coating cracked and carbonized Example 2 Coating cracked and carbonized Example 3 Coating cracked and carbonized Example 4 Coating cracked and carbonized Example 5 Slight swelling, local carbonization Example 6 Swelled but no cracking Example 7 Coating showed no significant changes, only surface slightly yellowed Example 8 Coating showed no changes at all

[0143] From the above results, the abrasion-resistant waterborne UV photocurable resin coating prepared by the application has good adhesion and abrasion resistance, and also has good flame-retardant fire resistance. Specifically, the abrasion loss of Example 1 without adding an abrasion-resistant agent reaches 1.92 mg, but due to the addition of nanoparticles, it has good adhesion and can reach 0 level, while in Example 2, the abrasion loss is reduced to 1.51 mg by directly adding unmodified nano-SiO2, but the adhesion is significantly reduced to 3 levels. This phenomenon shows that the theory of easy agglomeration and weak interfacial bonding of unmodified nanoparticles is consistent. In contrast, the abrasion loss of Example 3 is significantly reduced to 1.02 mg after adding the abrasion-resistant agent modified by the silane coupling agent, and the adhesion is restored to 1 level, verifying the key role of Si-O-Si covalent bond in improving the dispersibility of nanoparticles and the interfacial bonding strength. The addition of epoxy-modified in Example 4 forms stable ester bond / ether bond between the filler and the resin through ring-opening reaction, which further reduces the abrasion loss to 0.80 mg, indicating that the chemical bonding network is more efficient than physical adsorption. The introduction of phosphorus modification in Example 5 not only gives the material flame retardancy, but also changes the coating from cracking and carbonization to slight expansion, and further reduces the abrasion loss to 0.63 mg through the lubricating effect of phosphate groups, highlighting the synergistic effect of multifunctional modification. The amino acid grafting in Example 6 further strengthens the interfacial bonding through ionic bonding between amino groups / carboxyl groups and the resin, making the abrasion loss as low as 0.45 mg and the adhesion reaching the optimal 0 level. The flame retardant performance test shows that the phosphorus modification in Examples 5-6 significantly improves the high-temperature stability of the coating, changing from local carbonization to expansion without cracking, while Examples 7-8 use the introduction of boron nitride to further improve the flame-retardant fire resistance of the resin by endothermic decomposition, achieving no obvious change. The abrasion loss of Example 8 is the lowest at 0.34 mg, indicating that the topological entanglement of rigid nano-network and flexible resin chain not only effectively disperses mechanical stress, but also blocks heat transfer, thereby simultaneously optimizing the abrasion resistance and flame retardant performance.

Claims

1. A method for preparing a wear-resistant water-based UV-curable resin, characterized in that, Includes the following steps: (1) In an inert gas atmosphere, diisocyanate, polymeric polyol, catalyst and organic solvent are mixed and reacted at 60-90℃ for 1-4h; (2) Cool down to 50-70℃, add carboxylic acid chain extender and continue the reaction for 1-3h, then raise the temperature to 80-90℃, add hydroxyl compound, amine chain extender, catalyst and organic solvent and react for 2-4h; finally, lower the temperature to 70-80℃, add polymerization inhibitor, wear-resistant ethanol solution, hydroxypropyl methacrylate and catalyst and react for 1-3h to obtain a mixed solution; (3) Cool the mixed solution to 20-40℃, add triethylamine and water, stir to emulsify, add hot water at 50-90℃, remove solvent under reduced pressure, and obtain wear-resistant waterborne UV-curable resin. The hydroxyl compounds include one or a combination of at least two of hydroxyethyl acrylate, hydroxypropyl methacrylate, or hydroxypropyl acrylate. The method for preparing the wear-resistant agent is as follows: S1. Epoxy resin and organic solvent are mixed to form a dispersion. Isocyanate-based silane coupling agent is added and reacted. Phosphoric acid is added for phosphorus modification to obtain an epoxy-based phosphorus-modified silane coupling agent. S2. The nanoparticles are dispersed in an ethanol aqueous solution, the epoxy phosphorus modified silane coupling agent is added for surface modification, and then treated with an amino acid aqueous solution. After centrifugation and drying, the wear-resistant agent is obtained. The nanoparticles are at least one of silicon dioxide, aluminum oxide, calcium carbonate, or boron nitride, with a particle size of 20-200 nm; the amino acids are amino acids containing hydroxyl or thiol groups.

2. The preparation method of the wear-resistant waterborne UV-curable resin as described in claim 1, characterized in that, The polymerized polyol in step (1) includes any one or a combination of at least two of polycaprolactone triol, polytetrahydrofuran ether diol, polyethylene glycol, polypropylene glycol, polycaprolactone diol, or polycarbonate diol. The diisocyanate includes any one or at least two of hexamethylene diisocyanate, toluene diisocyanate, 4,4-diisocyanate dicyclohexylmethane, and isophorone diisocyanate.

3. The preparation method of the wear-resistant waterborne UV-curable resin as described in claim 1, characterized in that, The catalyst in step (1) or step (2) includes any one of dibutyltin dilaurate, stannous octoate, bismuth neodecanoate, and tetramethylbutanediamine.

4. The preparation method of the wear-resistant waterborne UV-curable resin as described in claim 1, characterized in that, The carboxyl chain extender in step (2) includes one or a combination of at least two of 2,2-dimethylolpropionic acid and 2,2-dimethylolbutyric acid; The amine chain extender includes any one or a combination of at least two of the following: ethylenediamine, propylenediamine, isofluranediamine, hydrazine hydrate, 2,4-toluenediamine, 2-methyl-1,5-pentanediamine, piperazine, or hexamethylenediamine.

5. The preparation method of the wear-resistant waterborne UV-curable resin as described in claim 1, characterized in that, The polymerization inhibitor in step (2) includes any one of hydroquinone, p-hydroxyanisole, and p-methoxyphenol.

6. The method for preparing the wear-resistant waterborne UV-curable resin as described in claim 1, characterized in that, The isocyanate-based silane coupling agent includes one or both of 3-isocyanate-propyltrimethoxysilane and propyltriethoxysilane.

7. The method for preparing the wear-resistant waterborne UV-curable resin as described in claim 1, characterized in that, Each component, by weight, includes: 5-10 parts of diisocyanate; 10-20 parts of polymerized polyol; Carboxylic acid chain extender 0.5-2 parts Hydroxyl compounds, 0.5-3 parts; 1-4 parts of amine chain extender; 0.5-10 parts of wear-resistant agent; 3-10 parts of acrylate monomer; Total catalyst amount: 0.01-0.1 parts; Total organic solvent content: 10-30 parts; 40-100 parts water.

8. A wear-resistant water-based UV-curable resin, characterized in that, It is obtained by any one of the preparation methods described in claims 1-7.

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