Bio-based UV resin and preparation method thereof

Abstract

The invention relates to the technical field of UV resin, and particularly discloses bio-based UV resin and a preparation method thereof, and the bio-based UV resin comprises the following raw materials: a bio-based benzoxazine monomer, epoxidized soybean oil, modified propolis, a reactive diluent and a photoinitiator; the preparation method comprises the following steps: stirring and mixing the reactive diluent and the photoinitiator to obtain a mixture; and under the protection of nitrogen, adding a bio-based benzoxazine monomer, epoxidized soybean oil, the modified propolis and the mixture into the reactor, and reacting at 70-80 DEG C for 1-3 hours to obtain the bio-based UV resin, the bio-based UV resin prepared by the invention has excellent thermal stability and chemical stability, excellent mechanical strength, high hardness, high flame retardance and excellent antibacterial property.

Description

Technical Field

[0001] The present application relates to the technical field of UV resins, and more specifically, to a bio-based UV resin and a preparation method thereof. Background Art

[0002] UV resin, also known as photosensitive resin, is an oligomer that can undergo physical and chemical changes rapidly in a short period of time after being exposed to light, and then cross-link and solidify.

[0003] The raw materials of traditional UV resins mainly rely on non-renewable resources such as fossil fuels (oil, coal), which have poor sustainability, high energy consumption, large carbon emissions, and increased environmental load. Bio-based UV resin is a renewable material whose raw materials mainly come from plants or animals. Compared with traditional fossil fuels, the production process of bio-based UV resins is more environmentally friendly and can reduce the consumption of earth resources.

[0004] However, at present, the bio-based UV resins on the market have the following problems: 1. The hardness and wear resistance of bio-based UV resins are not as good as traditional petroleum-based UV resins, which makes the product more susceptible to scratches or wear during use; 2. Bio-based UV resins show lower stability when facing chemicals such as acids, alkalis, and solvents, and are prone to degradation or deterioration; 3. The heat resistance of bio-based UV resins is generally lower than that of traditional petroleum-based UV resins; 4. Bio-based UV resins have poor flame retardancy because most bio-based materials contain a large amount of flammable organic components, and their molecular structure is relatively loose, which is prone to combustion reactions; 5. Most bio-based materials themselves do not have natural antibacterial functions, and their surface characteristics may be conducive to bacterial attachment and reproduction. Bio-based UV resins show lower antibacterial properties when facing microbial erosion.

[0005] Based on the above statements, the present application provides a bio-based UV resin and a preparation method thereof. Summary of the invention

[0006] In order to solve the problems raised in the background technology, the present application provides a bio-based UV resin and a preparation method thereof.

[0007] In the first aspect, the present application provides a bio-based UV resin, which adopts the following technical solution:

[0008] A bio-based UV resin comprises the following raw materials in parts by weight: 20-30 parts of bio-based benzoxazine monomers, 6-10 parts of epoxy soybean oil, 1-3 parts of modified propolis, 4-8 parts of active diluents, and 1-2 parts of photoinitiators.

[0009] Preferably, the bio-based benzoxazine monomer is prepared as follows:

[0010] A1. Place daidzein in dichloromethane and stir to obtain a dispersion, add acrylic acid, 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride to the dispersion under ice bath conditions, stir to react for 1-2 hours, heat to room temperature, stir to react for 8-12 hours, and obtain modified daidzein;

[0011] A2, placing resveratrol in dichloromethane and stirring to disperse to obtain a dispersion, adding maleic anhydride and phosphorus pentoxide to the dispersion under ice bath conditions, stirring to react for 1-2 hours, heating to room temperature, stirring to react for 4-8 hours, to obtain modified resveratrol;

[0012] A3. Place an amine compound and polyformaldehyde in an organic solvent, stir and react at 50-70° C. for 4-8 hours to obtain a mixture; add modified soybean aglycone, modified resveratrol and a catalyst to the mixture, stir and react at 70-90° C. for 18-24 hours, remove the organic solvent by vacuum distillation, and dry to obtain the desired bio-based benzoxazine monomer.

[0013] Preferably, in step A1, the weight ratio of daidzein, dichloromethane, acrylic acid, 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride is 1-2:5-8:2-3:0.2-0.4:0.1-0.3.

[0014] Preferably, in step A2, the mass ratio of resveratrol, dichloromethane, maleic anhydride and phosphorus pentoxide is 1-2:5-8:2-4:0.1-0.3.

[0015] Preferably, in step A3, the amine compound is prepared by compounding dehydroabietin amine and menthane diamine in a mass ratio of 2-4:1-2; the organic solvent is dioxane or toluene; the catalyst is p-toluenesulfonic acid; and the mass ratio of the amine compound, paraformaldehyde, organic solvent, modified daidzein, modified resveratrol and catalyst is 4-6:2-3:10-14:2-3:1-2:0.1-0.3.

[0016] Preferably, the modified propolis is prepared as follows:

[0017] B1. Freeze and crush propolis and sieve to obtain propolis powder, soak the propolis powder in an ethanol solution for 24-34 hours, centrifuge, collect the supernatant, and concentrate the supernatant at 20-30° C. using a rotary evaporator to obtain a propolis extract;

[0018] B2. Place the propolis extract in an organic solvent, add a catalyst and stir to obtain a dispersion, add acryloyl chloride to the dispersion in an ice bath, stir to react for 3-5 hours, then add a 10-hydroxy-2-decenoic acid derivative, stir to react at 60-80°C for 1-3 hours, and remove the organic solvent by rotary evaporation to obtain the desired modified propolis.

[0019] Preferably, in step B1, the mass ratio of propolis powder to ethanol solution is 1-2:6-10.

[0020] Preferably, in step B2, the organic solvent is ethyl acetate and the catalyst is 4-dimethylaminopyridine.

[0021] Preferably, the mass ratio of the propolis extract, the organic solvent, the catalyst, acryloyl chloride and the 10-hydroxy-2-decenoic acid derivative is 1-2:6-10:0.1-0.3:2-4:0.4-0.8.

[0022] Preferably, the preparation of the 10-hydroxy-2-decenoic acid derivative in step B2 is as follows: 10-hydroxy-2-decenoic acid and propionic anhydride are mixed in a mass ratio of 8-10:4-6, and stirred at 60-70°C for 2-4h to obtain a 10-hydroxy-2-decenoic acid derivative.

[0023] Preferably, the reactive diluent is a composition of trimethylolpropane triacrylate and pentaerythritol tetraacrylate in a mass ratio of 3-7:2-4.

[0024] Preferably, the photoinitiator is photoinitiator 1173.

[0025] In a second aspect, the present application provides a method for preparing a bio-based UV resin, using the following technical solution:

[0026] A method for preparing a bio-based UV resin comprises the following steps:

[0027] The active diluent and the photoinitiator are stirred and mixed to obtain a mixture; under the protection of nitrogen, the bio-based benzoxazine monomer, epoxy soybean oil, modified propolis and the mixture are added into the reactor, and the reaction is carried out at 70-80° C. for 1-3 hours to obtain the desired bio-based UV resin.

[0028] In summary, this application has the following beneficial effects:

[0029] The amine compound in the bio-based benzoxazine monomer prepared in this application is obtained by compounding dehydroabietamine and menthane diamine. Dehydroabietamine has excellent thermal stability and chemical stability. The molecule contains a phenanthrene ring structure, which can enhance the cross-linking density of the material, improve the mechanical strength and hardness, and improve the flame retardant properties of the material, and reduce the heat release rate during combustion. Menthane diamine can increase the cross-linking density of the material, enhance the mechanical properties, and increase the flexibility, thereby improving the impact strength and toughness of the material. When dehydroabietamine is compounded with menthane diamine, the final benzoxazine monomer has good mechanical properties, high hardness, heat resistance and chemical corrosion resistance, and at the same time has certain flexibility and impact resistance, which is suitable for long-term use in a variety of harsh environments.

[0030] The present application uses acrylic acid to modify soybean aglycone to obtain modified soybean aglycone, and uses maleic anhydride to modify resveratrol to obtain modified resveratrol; modified soybean aglycone and modified resveratrol are used as raw materials for preparing bio-based benzoxazine monomers, and the phenolic hydroxyl groups in the modified soybean aglycone and modified resveratrol can form more cross-linking points during the curing process, construct a denser three-dimensional network structure, and significantly improve the mechanical strength and chemical resistance of the material; the polyphenol structure of the modified soybean aglycone and the bisphenol structure of the modified resveratrol work together to make the material have better heat resistance and flame retardancy.

[0031] The present application freezes and crushes propolis and soaks it to obtain a propolis extract, adds acryloyl chloride and 10-hydroxy-2-decenoic acid derivatives to modify the propolis extract, and obtains a modified propolis. Propolis extract itself has a broad spectrum of antibacterial activity, and the modified propolis can better maintain this property. The acrylate functional group introduced by acryloyl chloride enhances the compatibility of propolis with bio-based UV resin, making the antibacterial components more evenly distributed throughout the system. The 10-hydroxy-2-decenoic acid propionate derivative further enhances the antibacterial effect, ensuring that the material can still maintain efficient antibacterial ability after long-term use. The acrylate functional group in propolis and the 10-hydroxy-2-decenoic acid derivative work together to enhance the mechanical strength, wear resistance and chemical resistance of the bio-based UV resin, forming a denser network structure. DETAILED DESCRIPTION

[0032] The present application is further described in detail below with reference to the embodiments.

[0033] The soybean aglycone used in the examples and comparative examples of the present application was purchased from Chengdu Ruifensidedan Biotechnology Co., Ltd. with the item number D-016; resveratrol was purchased from Chengdu Ruifensidedan Biotechnology Co., Ltd. with the item number B-002; paraformaldehyde was purchased from Merck Millipore with the item number 8.18715; dehydroabietin amine was purchased from Shanghai Yuanye Biotechnology Co., Ltd. with the item number S54367; menthane diamine was purchased from Wuhan Kamik Technology Co., Ltd.; propolis was purchased from Xinyang Mufan Biotechnology Co., Ltd.; 10-hydroxy-2-decenoic acid was purchased from Jinan Hongshengdi New Materials Co., Ltd.

[0034] Embodiment 1-3 provides a bio-based UV resin and a preparation method thereof.

[0035] Example 1

[0036] A bio-based UV resin comprises the following raw materials in parts by weight: 20 parts of bio-based benzoxazine monomer, 1 part of modified propolis, 4 parts of active diluent, and 1 part of photoinitiator. The active diluent is a composition of trimethylolpropane triacrylate and pentaerythritol tetraacrylate in a mass ratio of 3:2; and the photoinitiator is photoinitiator 1173.

[0037] The preparation of bio-based benzoxazine monomer is as follows:

[0038] A1, placing daidzein in dichloromethane and stirring and dispersing at a speed of 80 rpm to obtain a dispersion, adding acrylic acid, 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride to the dispersion under ice bath conditions, stirring and reacting at a speed of 80 rpm for 1 hour, heating to room temperature, stirring and reacting at a speed of 80 rpm for 8 hours to obtain modified daidzein; wherein the weight ratio of daidzein, dichloromethane, acrylic acid, 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride is 1:5:2:0.2:0.1;

[0039] A2, placing resveratrol in dichloromethane and stirring and dispersing at a rate of 80 rpm to obtain a dispersion, adding maleic anhydride and phosphorus pentoxide to the dispersion under ice bath conditions, stirring and reacting at 80 rpm for 1 hour, heating to room temperature, stirring and reacting at 80 rpm for 4 hours to obtain modified resveratrol; wherein the mass ratio of resveratrol, dichloromethane, maleic anhydride and phosphorus pentoxide is 1:5:2:0.1;

[0040] A3. Place an amine compound and polyformaldehyde in an organic solvent, stir and react at 50°C at 80rpm for 4h to obtain a mixture; add modified soybean aglycone, modified resveratrol and a catalyst to the mixture, stir and react at 70°C at 80rpm for 18h, remove the organic solvent by reduced pressure distillation, and dry to obtain the desired bio-based benzoxazine monomer; wherein the amine compound is obtained by compounding dehydroabietin amine and menthane diamine in a mass ratio of 2:1; the organic solvent is dioxane; the catalyst is p-toluenesulfonic acid; the mass ratio of the amine compound, polyformaldehyde, organic solvent, modified soybean aglycone, modified resveratrol and catalyst is 4:2:10:2:1:0.1.

[0041] The preparation of modified propolis is as follows:

[0042] B1. Freeze propolis at -20°C for 20 hours, crush and pass through an 80-mesh sieve to obtain propolis powder, soak the propolis powder in a 50% ethanol solution for 24 hours to obtain a mixed solution, centrifuge the mixed solution at 10,000 rpm for 3 minutes, collect the supernatant, and concentrate the supernatant to 0.1 times the volume at 20°C using a rotary evaporator to obtain a propolis extract; wherein the mass ratio of propolis powder to ethanol solution is 1:6;

[0043] B2, mixing 10-hydroxy-2-decenoic acid and propionic anhydride in a mass ratio of 8:4, stirring at 60° C. and 80 rpm for 2 h to obtain a 10-hydroxy-2-decenoic acid derivative;

[0044] B3, the propolis extract was placed in ethyl acetate, and then 4-dimethylaminopyridine was added, and the dispersion was obtained by stirring at a rate of 80 rpm for 20 min, and acryloyl chloride was added to the dispersion under ice bath conditions at a rate of 2 mL / min. After the addition was completed, the reaction was continued at a rate of 80 rpm for 3 h, and then 10-hydroxy-2-decenoic acid derivative was added, and the reaction was stirred at a rate of 80 rpm at 60 ° C for 1 h, and the modified propolis was obtained after removing ethyl acetate by rotary evaporation. The mass ratio of propolis extract, ethyl acetate, 4-dimethylaminopyridine, acryloyl chloride and 10-hydroxy-2-decenoic acid derivative was 1:6:0.1:2:0.4.

[0045] A bio-based UV resin is prepared as follows:

[0046] The active diluent and the photoinitiator are stirred and mixed to obtain a mixture; under the protection of nitrogen, the bio-based benzoxazine monomer, epoxy soybean oil, modified propolis and the mixture are added into the reactor, and the reaction is carried out at 70° C. for 1 hour to obtain the desired bio-based UV resin.

[0047] Example 2

[0048] A bio-based UV resin comprises the following raw materials in parts by weight: 25 parts of bio-based benzoxazine monomer, 2 parts of modified propolis, 6 parts of active diluent, and 1.5 parts of photoinitiator, wherein the active diluent is a composition of trimethylolpropane triacrylate and pentaerythritol tetraacrylate in a mass ratio of 5:3; and the photoinitiator is photoinitiator 1173.

[0049] The preparation of bio-based benzoxazine monomer is as follows:

[0050] A1, placing daidzein in dichloromethane and stirring and dispersing at a speed of 90 rpm to obtain a dispersion, adding acrylic acid, 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride to the dispersion under ice bath conditions, stirring and reacting at a speed of 90 rpm for 1.5 hours, heating to room temperature, stirring and reacting at a speed of 90 rpm for 10 hours to obtain modified daidzein; wherein the weight ratio of daidzein, dichloromethane, acrylic acid, 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride is 1.5:6.5:2.5:0.3:0.2;

[0051] A2, placing resveratrol in dichloromethane and stirring and dispersing at a rate of 90 rpm to obtain a dispersion, adding maleic anhydride and phosphorus pentoxide to the dispersion under ice bath conditions, stirring and reacting at 90 rpm for 1.5 hours, heating to room temperature, stirring and reacting at 90 rpm for 6 hours to obtain modified resveratrol; wherein the mass ratio of resveratrol, dichloromethane, maleic anhydride and phosphorus pentoxide is 1.5:6.5:3:0.2;

[0052] A3. Place an amine compound and polyformaldehyde in an organic solvent, stir and react at 60°C at 90rpm for 6h to obtain a mixture; add modified soybean aglycone, modified resveratrol and a catalyst to the mixture, stir and react at 80°C at 90rpm for 21h, remove the organic solvent by reduced pressure distillation, and dry to obtain the desired bio-based benzoxazine monomer; wherein the amine compound is obtained by compounding dehydroabietin amine and menthane diamine in a mass ratio of 3:1.5; the organic solvent is dioxane; the catalyst is p-toluenesulfonic acid; the mass ratio of the amine compound, polyformaldehyde, organic solvent, modified soybean aglycone, modified resveratrol and catalyst is 5:2.5:12:2.5:1.5:0.2.

[0053] The preparation of modified propolis is as follows:

[0054] B1. Freeze propolis at minus 19°C for 25 hours, crush and pass through a 90-mesh sieve to obtain propolis powder, soak the propolis powder in a 60% ethanol solution for 29 hours to obtain a mixed solution, centrifuge the mixed solution at 11000 rpm for 4 minutes, collect the supernatant, and concentrate the supernatant to 0.2 times the volume by a rotary evaporator at 25°C to obtain a propolis extract; wherein the mass ratio of propolis powder to ethanol solution is 1.5:8;

[0055] B2, mixing 10-hydroxy-2-decenoic acid and propionic anhydride in a mass ratio of 9:5, stirring at 65° C. and 90 rpm for 3 h to obtain a 10-hydroxy-2-decenoic acid derivative;

[0056] B3, the propolis extract was placed in ethyl acetate, and then 4-dimethylaminopyridine was added, and the dispersion was obtained by stirring at a rate of 90 rpm for 30 min, and acryloyl chloride was added to the dispersion under ice bath conditions at a rate of 3 mL / min. After the addition was completed, the reaction was continued at a rate of 90 rpm for 4 h, and then 10-hydroxy-2-decenoic acid derivative was added, and the reaction was stirred at a rate of 90 rpm at 70 ° C for 2 h, and the modified propolis was obtained after removing ethyl acetate by rotary evaporation. The mass ratio of propolis extract, ethyl acetate, 4-dimethylaminopyridine, acryloyl chloride and 10-hydroxy-2-decenoic acid derivative was 1.5:8:0.2:3:0.6.

[0057] A bio-based UV resin is prepared as follows:

[0058] The active diluent and the photoinitiator are stirred and mixed to obtain a mixture; under the protection of nitrogen, the bio-based benzoxazine monomer, epoxy soybean oil, modified propolis and the mixture are added into the reactor, and the mixture is reacted at 75° C. for 2 hours to obtain the desired bio-based UV resin.

[0059] Example 3

[0060] A bio-based UV resin comprises the following raw materials in parts by weight: 30 parts of bio-based benzoxazine monomer, 3 parts of modified propolis, 8 parts of active diluent, and 2 parts of photoinitiator, wherein the active diluent is a composition of trimethylolpropane triacrylate and pentaerythritol tetraacrylate in a mass ratio of 7:4; and the photoinitiator is photoinitiator 1173.

[0061] The preparation of bio-based benzoxazine monomer is as follows:

[0062] A1, placing daidzein in dichloromethane and stirring and dispersing at a rate of 100 rpm to obtain a dispersion, adding acrylic acid, 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride to the dispersion under ice bath conditions, stirring and reacting at a rate of 100 rpm for 2 hours, heating to room temperature, stirring and reacting at a rate of 100 rpm for 12 hours to obtain modified daidzein; wherein the weight ratio of daidzein, dichloromethane, acrylic acid, 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride is 2:8:3:0.4:0.3;

[0063] A2, placing resveratrol in dichloromethane and stirring and dispersing at a rate of 100 rpm to obtain a dispersion, adding maleic anhydride and phosphorus pentoxide to the dispersion under ice bath conditions, stirring and reacting at 100 rpm for 2 hours, heating to room temperature, stirring and reacting at 100 rpm for 8 hours to obtain modified resveratrol; wherein the mass ratio of resveratrol, dichloromethane, maleic anhydride and phosphorus pentoxide is 2:8:4:0.3;

[0064] A3. Place an amine compound and polyformaldehyde in an organic solvent, stir and react at 70°C at a rate of 100 rpm for 8 hours to obtain a mixture; add modified soybean aglycone, modified resveratrol and a catalyst to the mixture, stir and react at 90°C at a rate of 100 rpm for 24 hours, remove the organic solvent by reduced pressure distillation, and dry to obtain the desired bio-based benzoxazine monomer; wherein the amine compound is obtained by compounding dehydroabietin amine and menthane diamine in a mass ratio of 4:2; the organic solvent is toluene; the catalyst is p-toluenesulfonic acid; the mass ratio of the amine compound, polyformaldehyde, organic solvent, modified soybean aglycone, modified resveratrol and catalyst is 6:3:14:3:2:0.3.

[0065] The preparation of modified propolis is as follows:

[0066] B1. Freeze propolis at -18°C for 30h, crush through a 100-mesh sieve to obtain propolis powder, soak the propolis powder in a 70% ethanol solution for 34h to obtain a mixed solution, centrifuge the mixed solution at 12000rpm for 5min, collect the supernatant, and concentrate the supernatant to 0.3 times of its volume at 30°C by a rotary evaporator to obtain a propolis extract; wherein the mass ratio of propolis powder to ethanol solution is 2:10;

[0067] B2, 10-hydroxy-2-decenoic acid and propionic anhydride were mixed in a mass ratio of 10:6, and the mixture was stirred at 70° C. and 100 rpm for 4 h to obtain a 10-hydroxy-2-decenoic acid derivative;

[0068] B3, the propolis extract is placed in ethyl acetate, and then 4-dimethylaminopyridine is added, and the dispersion is obtained by stirring at a rate of 100 rpm for 40 min, and acryloyl chloride is added to the dispersion under the condition of an ice bath, and the rate of dropping is 4 mL / min. After the dropwise addition is completed, the reaction is continued at a rate of 100 rpm for 5 h, and then a 10-hydroxy-2-decenoic acid derivative is added, and the reaction is stirred at a rate of 100 rpm for 3 h at 80 ° C, and the modified propolis is obtained after removing ethyl acetate by rotary evaporation. The mass ratio of propolis extract, ethyl acetate, 4-dimethylaminopyridine, acryloyl chloride and 10-hydroxy-2-decenoic acid derivative is 2:10:0.3:4:0.8.

[0069] A bio-based UV resin is prepared as follows:

[0070] The active diluent and the photoinitiator are stirred and mixed to obtain a mixture; under the protection of nitrogen, the bio-based benzoxazine monomer, epoxy soybean oil, modified propolis and the mixture are added into the reactor, and the reaction is carried out at 80° C. for 3 hours to obtain the desired bio-based UV resin.

[0071] In order to verify the comprehensive performance of the bio-based UV resin prepared in Examples 1-3 of the present application, the present application sets up Comparative Examples 1-8, which are as follows:

[0072] Comparative Example 1

[0073] Comparative Example 1 is the same as Example 1, except that daidzein is not modified in the preparation of the bio-based benzoxazine monomer, as follows:

[0074] The preparation of bio-based benzoxazine monomer is as follows:

[0075] A1. Place resveratrol in dichloromethane and stir and disperse at a rate of 80 rpm to obtain a dispersion, add maleic anhydride and phosphorus pentoxide to the dispersion under ice bath conditions, stir and react at 80 rpm for 1 hour, heat to room temperature, stir and react at 80 rpm for 4 hours to obtain modified resveratrol; wherein the mass ratio of resveratrol, dichloromethane, maleic anhydride and phosphorus pentoxide is 1:5:2:0.1;

[0076] A2. Place an amine compound and polyformaldehyde in an organic solvent, stir and react at 50°C at 80 rpm for 4 hours to obtain a mixture; add soybean aglycone, modified resveratrol and a catalyst to the mixture, stir and react at 70°C at 80 rpm for 18 hours, remove the organic solvent by reduced pressure distillation, and dry to obtain the desired bio-based benzoxazine monomer; wherein the amine compound is obtained by compounding dehydroabietin amine and menthane diamine in a mass ratio of 2:1; the organic solvent is dioxane; the catalyst is p-toluenesulfonic acid; the mass ratio of the amine compound, polyformaldehyde, organic solvent, soybean aglycone, modified resveratrol and catalyst is 4:2:10:2:1:0.1.

[0077] Comparative Example 2

[0078] Comparative Example 2 is the same as Example 1, except that resveratrol is not modified in the preparation of the bio-based benzoxazine monomer, as follows:

[0079] The preparation of bio-based benzoxazine monomer is as follows:

[0080] A1, placing daidzein in dichloromethane and stirring and dispersing at a speed of 80 rpm to obtain a dispersion, adding acrylic acid, 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride to the dispersion under ice bath conditions, stirring and reacting at a speed of 80 rpm for 1 hour, heating to room temperature, stirring and reacting at a speed of 80 rpm for 8 hours to obtain modified daidzein; wherein the weight ratio of daidzein, dichloromethane, acrylic acid, 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride is 1:5:2:0.2:0.1;

[0081] A2. Place an amine compound and polyformaldehyde in an organic solvent, stir and react at 50°C at 80rpm for 4h to obtain a mixture; add modified soybean aglycone, resveratrol and a catalyst to the mixture, stir and react at 70°C at 80rpm for 18h, remove the organic solvent by reduced pressure distillation, and dry to obtain the desired bio-based benzoxazine monomer; wherein the amine compound is obtained by compounding dehydroabietin amine and menthane diamine in a mass ratio of 2:1; the organic solvent is dioxane; the catalyst is p-toluenesulfonic acid; the mass ratio of the amine compound, polyformaldehyde, organic solvent, modified soybean aglycone, resveratrol and catalyst is 4:2:10:2:1:0.1.

[0082] Comparative Example 3

[0083] Comparative Example 3 is the same as Example 1, except that modified daidzein is not added in the preparation of the bio-based benzoxazine monomer, as follows:

[0084] The preparation of bio-based benzoxazine monomer is as follows:

[0085] A1. Place resveratrol in dichloromethane and stir and disperse at a rate of 80 rpm to obtain a dispersion, add maleic anhydride and phosphorus pentoxide to the dispersion under ice bath conditions, stir and react at 80 rpm for 1 hour, heat to room temperature, stir and react at 80 rpm for 4 hours to obtain modified resveratrol; wherein the mass ratio of resveratrol, dichloromethane, maleic anhydride and phosphorus pentoxide is 1:5:2:0.1;

[0086] A3. Place an amine compound and polyformaldehyde in an organic solvent, stir and react at 50°C at 80 rpm for 4 hours to obtain a mixture; add modified resveratrol and a catalyst to the mixture, stir and react at 70°C at 80 rpm for 18 hours, remove the organic solvent by reduced pressure distillation, and dry to obtain the desired bio-based benzoxazine monomer; wherein the amine compound is obtained by compounding dehydroabietin amine and menthane diamine in a mass ratio of 2:1; the organic solvent is dioxane; the catalyst is p-toluenesulfonic acid; the mass ratio of the amine compound, polyformaldehyde, organic solvent, modified resveratrol and catalyst is 4:2:10:3:0.1.

[0087] Comparative Example 4

[0088] Comparative Example 4 is the same as Example 1, except that modified resveratrol is not added in the preparation of the bio-based benzoxazine monomer, as follows:

[0089] The preparation of bio-based benzoxazine monomer is as follows:

[0090] A1, placing daidzein in dichloromethane and stirring and dispersing at a speed of 80 rpm to obtain a dispersion, adding acrylic acid, 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride to the dispersion under ice bath conditions, stirring and reacting at a speed of 80 rpm for 1 hour, heating to room temperature, stirring and reacting at a speed of 80 rpm for 8 hours to obtain modified daidzein; wherein the weight ratio of daidzein, dichloromethane, acrylic acid, 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride is 1:5:2:0.2:0.1;

[0091] A2. Place an amine compound and polyformaldehyde in an organic solvent, stir and react at 50°C at 80 rpm for 4 hours to obtain a mixture; add modified soybean aglycone and a catalyst to the mixture, stir and react at 70°C at 80 rpm for 18 hours, remove the organic solvent by reduced pressure distillation, and dry to obtain the desired bio-based benzoxazine monomer; wherein the amine compound is obtained by compounding dehydroabietin amine and menthane diamine in a mass ratio of 2:1; the organic solvent is dioxane; the catalyst is p-toluenesulfonic acid; the mass ratio of the amine compound, polyformaldehyde, organic solvent, modified soybean aglycone and catalyst is 4:2:10:3:0.1.

[0092] Comparative Example 5

[0093] Comparative Example 5 is the same as Example 1, except that dehydroabietinamine is not added in the preparation of the bio-based benzoxazine monomer, as follows:

[0094] The preparation of bio-based benzoxazine monomer is as follows:

[0095] A1, placing daidzein in dichloromethane and stirring and dispersing at a speed of 80 rpm to obtain a dispersion, adding acrylic acid, 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride to the dispersion under ice bath conditions, stirring and reacting at a speed of 80 rpm for 1 hour, heating to room temperature, stirring and reacting at a speed of 80 rpm for 8 hours to obtain modified daidzein; wherein the weight ratio of daidzein, dichloromethane, acrylic acid, 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride is 1:5:2:0.2:0.1;

[0096] A2, placing resveratrol in dichloromethane and stirring and dispersing at a rate of 80 rpm to obtain a dispersion, adding maleic anhydride and phosphorus pentoxide to the dispersion under ice bath conditions, stirring and reacting at 80 rpm for 1 hour, heating to room temperature, stirring and reacting at 80 rpm for 4 hours to obtain modified resveratrol; wherein the mass ratio of resveratrol, dichloromethane, maleic anhydride and phosphorus pentoxide is 1:5:2:0.1;

[0097] A3. Place an amine compound and polyformaldehyde in an organic solvent, stir and react at 50°C at 80 rpm for 4 hours to obtain a mixture; add modified soybean aglycone, modified resveratrol and a catalyst to the mixture, stir and react at 70°C at 80 rpm for 18 hours, remove the organic solvent by reduced pressure distillation, and dry to obtain the desired bio-based benzoxazine monomer; wherein the amine compound is menthane diamine; the organic solvent is dioxane; the catalyst is p-toluenesulfonic acid; the mass ratio of the amine compound, polyformaldehyde, organic solvent, modified soybean aglycone, modified resveratrol and catalyst is 4:2:10:2:1:0.1.

[0098] Comparative Example 6

[0099] Comparative Example 6 is the same as Example 1, except that no menthane diamine is added in the preparation of the bio-based benzoxazine monomer, as follows:

[0100] The preparation of bio-based benzoxazine monomer is as follows:

[0101] A1, placing daidzein in dichloromethane and stirring and dispersing at a speed of 80 rpm to obtain a dispersion, adding acrylic acid, 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride to the dispersion under ice bath conditions, stirring and reacting at a speed of 80 rpm for 1 hour, heating to room temperature, stirring and reacting at a speed of 80 rpm for 8 hours to obtain modified daidzein; wherein the weight ratio of daidzein, dichloromethane, acrylic acid, 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride is 1:5:2:0.2:0.1;

[0102] A2, placing resveratrol in dichloromethane and stirring and dispersing at a rate of 80 rpm to obtain a dispersion, adding maleic anhydride and phosphorus pentoxide to the dispersion under ice bath conditions, stirring and reacting at 80 rpm for 1 hour, heating to room temperature, stirring and reacting at 80 rpm for 4 hours to obtain modified resveratrol; wherein the mass ratio of resveratrol, dichloromethane, maleic anhydride and phosphorus pentoxide is 1:5:2:0.1;

[0103] A3. Place an amine compound and polyformaldehyde in an organic solvent, stir and react at 50°C at 80 rpm for 4 hours to obtain a mixture; add modified soybean aglycone, modified resveratrol and a catalyst to the mixture, stir and react at 70°C at 80 rpm for 18 hours, remove the organic solvent by reduced pressure distillation, and dry to obtain the desired bio-based benzoxazine monomer; wherein the amine compound is dehydroabietin amine; the organic solvent is dioxane; the catalyst is p-toluenesulfonic acid; the mass ratio of the amine compound, polyformaldehyde, organic solvent, modified soybean aglycone, modified resveratrol and catalyst is 4:2:10:2:1:0.1.

[0104] Comparative Example 7

[0105] Comparative Example 7 is the same as Example 1, except that acryloyl chloride is not added in the preparation of the modified propolis, specifically as follows:

[0106] The preparation of modified propolis is as follows:

[0107] B1. Freeze propolis at -20°C for 20 hours, crush and pass through an 80-mesh sieve to obtain propolis powder, soak the propolis powder in a 50% ethanol solution for 24 hours to obtain a mixed solution, centrifuge the mixed solution at 10,000 rpm for 3 minutes, collect the supernatant, and concentrate the supernatant to 0.1 times the volume at 20°C using a rotary evaporator to obtain a propolis extract; wherein the mass ratio of propolis powder to ethanol solution is 1:6;

[0108] B2, mixing 10-hydroxy-2-decenoic acid and propionic anhydride in a mass ratio of 8:4, stirring at 60° C. and 80 rpm for 2 h to obtain a 10-hydroxy-2-decenoic acid derivative;

[0109] B3, placing the propolis extract in ethyl acetate, adding 4-dimethylaminopyridine, stirring at 80 rpm for 20 min to obtain a dispersion, adding 10-hydroxy-2-decenoic acid derivative to the dispersion, stirring at 80 rpm for 1 h at 60°C, and removing ethyl acetate by rotary evaporation to obtain modified propolis. The mass ratio of propolis extract, ethyl acetate, 4-dimethylaminopyridine and 10-hydroxy-2-decenoic acid derivative is 1:6:0.1:0.4.

[0110] Comparative Example 8

[0111] Comparative Example 8 is the same as Example 1, except that no 10-hydroxy-2-decenoic acid derivative is added in the preparation of the modified propolis, specifically as follows:

[0112] The preparation of modified propolis is as follows:

[0113] B1. Freeze propolis at -20°C for 20 hours, crush and pass through an 80-mesh sieve to obtain propolis powder, soak the propolis powder in a 50% ethanol solution for 24 hours to obtain a mixed solution, centrifuge the mixed solution at 10,000 rpm for 3 minutes, collect the supernatant, and concentrate the supernatant to 0.1 times the volume at 20°C using a rotary evaporator to obtain a propolis extract; wherein the mass ratio of propolis powder to ethanol solution is 1:6;

[0114] B2, the propolis extract is placed in ethyl acetate, 4-dimethylaminopyridine is added, and the dispersion is obtained by stirring at a rate of 80rpm for 20min, and acryloyl chloride is added dropwise to the dispersion under the condition of an ice bath, and the rate of dropping is 2mL / min. After the dropwise addition is completed, the reaction is continued to be stirred at a rate of 80rpm for 3h, and the modified propolis is obtained after the ethyl acetate is removed by rotary evaporation. The mass ratio of propolis extract, ethyl acetate, 4-dimethylaminopyridine and acryloyl chloride is 1:6:0.1:2.

[0115] Performance Testing

[0116] The comprehensive properties of the bio-based UV resins prepared in Examples 1-3 of the present application and Comparative Examples 1-8 were tested respectively.

[0117] The bio-based UV resins prepared in Examples 1-3 and Comparative Examples 1-8 of the present application were placed in molds respectively, and cured for 2 minutes in a UV curing machine with a power of 40 W and an UV light irradiation distance of 15 cm to obtain a bio-based UV resin cured film with a thickness of 50 μm.

[0118] 1. The tensile properties of bio-based UV resin cured films were tested according to GB / T 528-2009; the pencil hardness was tested according to GB / T 6736-2006;

[0119] 2. Chemical resistance determination: The bio-based UV resin cured films prepared in Examples 1-3 and Comparative Examples 1-8 were immersed in a NaOH solution with a mass concentration of 10% at room temperature, taken out after immersion for 48 hours, dried, and the tensile properties were tested according to the GB / T 528-2009 method;

[0120] 3. Thermal stability test: The thermal stability test of the bio-based UV resin cured films obtained in Examples 1-3 and Comparative Examples 1-8 was conducted using a TGA 1 thermogravimetric analyzer produced by a US PE factory. The test conditions were: in a nitrogen atmosphere, the temperature was raised from room temperature to the 5% thermal weight loss temperature of the bio-based UV resin cured film at a heating rate of 20°C / min, and thermogravimetric analysis was performed;

[0121] 4. Flame retardancy test: The bio-based UV resin cured films prepared in Examples 1-3 and Comparative Examples 1-8 were subjected to flame retardancy test using a UL-94 vertical / horizontal burning tester;

[0122] 5. Antibacterial properties: The test was conducted according to the method of GB / T 21866-2008, with Escherichia coli and Staphylococcus aureus as the test bacteria, and the bio-based UV resin cured films prepared in Examples 1-3 and Comparative Examples 1-8 as the experimental group.

[0123] The results are shown in the following table:

[0124]

[0125] As shown in the above table, the comprehensive performance of the bio-based UV resin prepared in Examples 1-3 is far superior to that of Comparative Examples 1-8, and has excellent thermal stability and chemical stability, excellent mechanical strength, high hardness, high flame retardancy and excellent antibacterial properties.

[0126] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A bio-based UV resin, characterized in that: The invention comprises the following raw materials in parts by weight: 20-30 parts of bio-based benzoxazine monomer, 6-10 parts of epoxy soybean oil, 1-3 parts of modified propolis, 4-8 parts of active diluent and 1-2 parts of photoinitiator.

2. The bio-based UV resin according to claim 1, characterized in that The preparation of the bio-based benzoxazine monomer is as follows: A1. Place daidzein in dichloromethane and stir to obtain a dispersion, add acrylic acid, 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride to the dispersion under ice bath conditions, stir to react for 1-2 hours, heat to room temperature, stir to react for 8-12 hours, and obtain modified daidzein; A2, placing resveratrol in dichloromethane and stirring to disperse to obtain a dispersion, adding maleic anhydride and phosphorus pentoxide to the dispersion under ice bath conditions, stirring to react for 1-2 hours, heating to room temperature, stirring to react for 4-8 hours, to obtain modified resveratrol; A3. Place an amine compound and polyformaldehyde in an organic solvent, stir and react at 50-70° C. for 4-8 hours to obtain a mixture; add modified soybean aglycone, modified resveratrol and a catalyst to the mixture, stir and react at 70-90° C. for 18-24 hours, remove the organic solvent by vacuum distillation, and dry to obtain the desired bio-based benzoxazine monomer.

3. The bio-based UV resin according to claim 2, characterized in that In the step A1, the weight ratio of daidzein, dichloromethane, acrylic acid, 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride is 1-2:5-8:2-3:0.2-0.4:0.1-0.3; and in the step A2, the weight ratio of resveratrol, dichloromethane, maleic anhydride and phosphorus pentoxide is 1-2:5-8:2-4:0.1-0.

3.

4. The bio-based UV resin according to claim 2, characterized in that In step A3, the amine compound is prepared by compounding dehydroabietin amine and menthane diamine in a mass ratio of 2-4:1-2; the organic solvent is dioxane or toluene; the catalyst is p-toluenesulfonic acid; and the mass ratio of the amine compound, paraformaldehyde, organic solvent, modified daidzein, modified resveratrol and catalyst is 4-6:2-3:10-14:2-3:1-2:0.1-0.

3.

5. The bio-based UV resin according to claim 1, characterized in that The preparation of the modified propolis is as follows: B1. Freeze and crush propolis and sieve to obtain propolis powder, soak the propolis powder in an ethanol solution for 24-34 hours, centrifuge, collect the supernatant, and concentrate the supernatant at 20-30° C. using a rotary evaporator to obtain a propolis extract; B2. Place the propolis extract in an organic solvent, add a catalyst and stir to obtain a dispersion, add acryloyl chloride to the dispersion in an ice bath, stir to react for 3-5 hours, then add a 10-hydroxy-2-decenoic acid derivative, stir to react at 60-80°C for 1-3 hours, and remove the organic solvent by rotary evaporation to obtain the desired modified propolis.

6. The bio-based UV resin according to claim 5, characterized in that The mass ratio of propolis powder to ethanol solution in step B1 is 1-2:6-10; the organic solvent in step B2 is ethyl acetate, and the catalyst is 4-dimethylaminopyridine; the mass ratio of propolis extract, organic solvent, catalyst, acryloyl chloride and 10-hydroxy-2-decenoic acid derivative is 1-2:6-10:0.1-0.3:2-4:0.4-0.

8.

7. The bio-based UV resin according to claim 5, characterized in that The preparation of the 10-hydroxy-2-decenoic acid derivative in step B2 is as follows: 10-hydroxy-2-decenoic acid and propionic anhydride are mixed in a mass ratio of 8-10:4-6, and stirred at 60-70° C. for reaction for 2-4 hours to obtain the 10-hydroxy-2-decenoic acid derivative.

8. The bio-based UV resin according to claim 1, characterized in that The active diluent is a composition of trimethylolpropane triacrylate and pentaerythritol tetraacrylate in a mass ratio of 3-7:2-4.

9. The bio-based UV resin according to claim 1, characterized in that The photoinitiator is photoinitiator 1173.

10. A method for preparing the bio-based UV resin according to any one of claims 1 to 9, characterized in that: The following steps are involved: The active diluent and the photoinitiator are stirred and mixed to obtain a mixture; under the protection of nitrogen, the bio-based benzoxazine monomer, epoxy soybean oil, modified propolis and the mixture are added into the reactor, and the reaction is carried out at 70-80° C. for 1-3 hours to obtain the desired bio-based UV resin.

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