Preparation method of hydrogenated rosin derivative

Abstract

The invention discloses a preparation method of a hydrogenated rosin derivative, and belongs to the technical field of rosin derivative preparation. Comprising the following steps: carrying out hydrogenation reaction on a rosin solution under the catalytic action of a catalyst to obtain hydrogenated rosin; and crushing the hydrogenated rosin, mixing the crushed hydrogenated rosin with glycidyl methacrylate, p-hydroxyanisole and triethylamine in a nitrogen atmosphere, and carrying out a heat preservation reaction to obtain the hydrogenated rosin derivative. The catalyst comprises a nickel-based active component and a hydrophilic and oleophylic carrier, the hydrophilic and lipophilic carrier comprises a hydrophilic mesoporous silica shell layer and a lipophilic molecular sieve core cavity; the conversion rate of rosin hydrogenation reaction is improved by introducing a hydrophilic and oleophylic catalyst; the coating prepared by using the hydrogenated rosin-based acrylate derivative prepared from hydrogenated rosin as a coating monomer has good hardness, bonding strength and wear resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of preparation of rosin derivatives, and in particular to a method for preparing a hydrogenated rosin derivative. Background Art

[0002] Rosin is a natural resin with remarkable thermoplastic properties. Its chemical composition is primarily composed of resin acids, along with some fatty acids and neutral substances. These components work together to enable rosin and its various derivatives to be widely used in industrial and commercial fields.

[0003] Because rosin molecules contain unsaturated conjugated double bonds, they are highly sensitive to oxygen. When exposed to oxygen, rosin is susceptible to oxidation, which can lead to a gradual decline in the performance of rosin materials, affecting their value. Therefore, to improve the practicality and stability of rosin, researchers and engineers have developed a variety of modification techniques, including isomerization, disproportionation, hydrogenation, maleation, and esterification. Through these treatments, rosin derivatives not only retain their original properties but also gain new functionalities, resulting in superior performance in various applications. Among its derivatives, hydrogenated rosin is an important modified material, produced through hydrogenation. Hydrogenated rosin exhibits excellent antioxidant properties, low brittleness, high thermal stability, and is non-toxic. Consequently, it has a wide range of industrial applications, such as adhesives, synthetic rubber, coatings, and inks.

[0004] Catalysts based on precious metals as active components have made significant progress in rosin hydrogenation. However, precious metals also have certain unavoidable drawbacks, such as high cost, limited availability, and instability, which significantly increase the cost of their industrial application. To address this issue, researchers have begun to focus on the development of non-precious metal catalysts, with nickel-based catalysts being the most widely used type, providing a reliable guarantee for the catalytic cracking and hydrogenation of rosin. To protect the ecological environment, there is increasing emphasis on the development of green chemistry and environmentally friendly chemistry. Since residual solvents after various chemical reactions can cause varying degrees of damage to the environment and human health, adhering to green chemistry principles, such as catalyst reuse and the use of green solvents, is particularly important. Solvents play a supporting role in the interaction between the support and the metal, as well as in the adsorption and desorption steps, and can therefore influence the selectivity and activity of the reaction, which can be attributed to the solvent's geometry and polarity. Researchers have previously tried using ethanol, n-octane, and other organic solvents as reaction solvents for catalytic hydrogenation. Although these organic solvents are widely used in chemical production, they can escape into the environment and cause the production of various atmospheric pollutants. Water has the advantages of being abundant and inexpensive, easily available, and easy to separate from the reaction mixture. In many cases, water as a solvent can not only accelerate the rate of organic reactions to a certain extent, but also improve the regioselectivity of chemical reactions. Due to the hydrophobicity of rosin hydrogenation catalysts, they have poor solubility or miscibility with water, which in turn leads to low yields. Therefore, how to improve the miscibility of rosin hydrogenation catalysts in water has become an important research direction. Summary of the Invention

[0005] The object of the present invention is to provide a method for preparing hydrogenated rosin derivatives, which is used to solve the problem of low reaction yield caused by poor miscibility and dispersibility of rosin hydrogenation catalyst in water in the prior art.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A method for preparing a hydrogenated rosin derivative, comprising the following steps:

[0008] S1, taking a rosin solution and performing a hydrogenation reaction under the catalytic action of a catalyst to obtain hydrogenated rosin;

[0009] S2, crushing the hydrogenated rosin, mixing it with glycidyl methacrylate, p-hydroxyanisole and triethylamine in a nitrogen atmosphere, and reacting at room temperature to obtain the hydrogenated rosin derivative;

[0010] The catalyst comprises a nickel-based active component and a hydrophilic and lipophilic carrier;

[0011] The hydrophilic and lipophilic carrier comprises a hydrophilic mesoporous silica shell layer and an lipophilic molecular sieve core cavity.

[0012] As a further embodiment of the present invention, the method for preparing the catalyst comprises the following steps:

[0013] A1. Cerium nitrate hexahydrate, deionized water, and sodium hydroxide are mixed, ultrasonically stirred, hydrothermally treated, cooled, centrifuged, the solid phase is washed, dried, and added to a sodium stearate-ethanol aqueous solution. The mixture is heated and stirred in a water bath, filtered, the solid phase is washed, and dried to obtain material A; rod-shaped cerium oxide is prepared by a hydrothermal synthesis method, and then the rod-shaped cerium oxide is lipophilically modified with sodium stearate to improve particle size dispersibility and stability, thereby obtaining rod-shaped cerium oxide with lipophilicity;

[0014] A2. Mix HY molecular sieve, material A, sesbania powder, sodium bicarbonate, and deionized water, extrusion molding, drying, and calcination to obtain material B; co-sinter the molecular sieve with oleophilic rod-shaped cerium oxide to impart good oleophilic properties to the inner cavity of the molecular sieve. At the same time, the rod-shaped cerium oxide is introduced to serve as an anchoring point for the nickel active component and, on the other hand, to promote electron migration and improve the catalytic efficiency;

[0015] A3, taking the material B and immersing it in an ammonium chloride solution, performing ammonium ion exchange, centrifuging, washing the solid phase, and drying to obtain material C;

[0016] A4. Mix the material C, polydimethyl ammonium chloride, and deionized water for surface modification, centrifuge, add the solid phase to the treatment solution, ultrasonicate, add tetraethyl orthosilicate, stir, filter, wash, dry, grind, and calcine to obtain the material D with a mesoporous silica-coated molecular sieve structure;

[0017] A5. Take the material D, nickel acetate, and anhydrous ethanol, mix them, ultrasonicate them, stir them, centrifuge them, wash the solid phase, vacuum dry them, grind them, and calcine them to obtain a hydrophilic and lipophilic catalyst loaded with active nickel.

[0018] As a further solution of the present invention, in step S1, the mass ratio of the rosin solution to the catalyst is 21-22:0.001-0.002.

[0019] As a further embodiment of the present invention, in step S2, the mass ratio of hydrogenated rosin, glycidyl methacrylate, p-hydroxyanisole, and triethylamine is 35-40:15-17:0.04-0.05:0.06-0.07.

[0020] As a further embodiment of the present invention, in step A1, the mass ratio of the cerium nitrate hexahydrate, deionized water, sodium hydroxide, and sodium stearate is 2.14-2.35:60-70:17.9-18.6:0.4-0.6; and the ethanol aqueous solution is prepared from 4 mL of ethanol and 16 mL of deionized water.

[0021] As a further solution of the present invention, in step A2, the mass ratio of the HY molecular sieve, material A, sesbania powder, sodium bicarbonate, and deionized water is 17-25:1.8-2.1:0.32-0.45:0.15-0.22:0.15-0.23:20-25.

[0022] As a further solution of the present invention, in step A3, the dosage ratio of the material B and the ammonium chloride solution is 1 g: 20-25 mL; and the concentration of the ammonium chloride solution is 1 mol / L.

[0023] As a further embodiment of the present invention, in step A4, the material C, polydialkylpropylenedimethylammonium chloride, deionized water, treatment liquid, and ethyl orthosilicate are prepared in a ratio of 3-4 g: 0.18-0.24 g: 50 mL: 300-400 mL: 3.8-4.8 g; and the treatment liquid is prepared by mixing 500 mL of ethanol, 3 g of hexadecyltrimethylammonium bromide, and 10 g of 28% ammonia water.

[0024] As a further solution of the present invention, in step A5, the dosage ratio of the material D, nickel acetate, and anhydrous ethanol is 0.25-0.35 g: 35-55 mg: 20-30 mL.

[0025] Beneficial effects of the present invention:

[0026] The present invention discloses a method for preparing a hydrogenated rosin derivative by providing a method for preparing a hydrophilic and lipophilic catalyst. The catalyst comprises an lipophilic molecular sieve as a core layer and a surface-coated hydrophilic mesoporous silica. The core layer and the shell layer have good pore connectivity. The smaller particle size and the formation of mesopores in the shell layer effectively enhance the mass transfer performance of the catalytic reaction and improve the yield of hydrogenated rosin. In addition, the use of a water-oil mixture as a solvent for the rosin is more environmentally friendly.

[0027] Furthermore, hydrogenated rosin is used to prepare hydrogenated rosin-based acrylate derivative monomers, and a triphenanthrene ring skeleton structure is introduced to improve the hardness, bonding strength and wear resistance of the prepared coating. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The present invention will be further described below with reference to the accompanying drawings.

[0029] Figure 1 is a SEM image of the catalyst prepared in Preparation Example 2 of the present invention;

[0030] Figure 2 is a TEM image of the catalyst prepared in Preparation Example 2 of the present invention;

[0031] Figure 3 Schematic diagram of the water drop contact angle of the catalyst prepared in Preparation Example 2 of the present invention. DETAILED DESCRIPTION

[0032] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0033] Preparation Example 1

[0034] A method for preparing a catalyst for catalyzing the hydrogenation of rosin to prepare hydrogenated rosin comprises the following steps:

[0035] A1. Mix cerium nitrate hexahydrate, deionized water, and sodium hydroxide, stir ultrasonically for 15 minutes, transfer to a hydrothermal reactor and maintain at 100°C for 20 hours, cool, centrifuge, wash the solid phase, dry, add to a sodium stearate-ethanol aqueous solution, heat and stir in a water bath at 60°C for 1 hour, filter, wash the solid phase, and dry to obtain material A; the mass ratio of the cerium nitrate hexahydrate, deionized water, sodium hydroxide, and sodium stearate is 2.14:60:17.9:0.4; the ethanol aqueous solution is prepared from 4 mL of ethanol and 16 mL of deionized water;

[0036] A2, take HY type molecular sieve (silicon aluminum ratio = 5, purchased from Guangdong Yunxing Biotechnology Co., Ltd.), material A, sesbania powder, sodium bicarbonate, and deionized water, mix evenly, knead 3 times in a twin-screw extruder and then extrude into strips. The template uses a 2.0 mm cylindrical template, dry, and calcine at 450 ° C for 3 h to obtain material B; the mass ratio of the HY type molecular sieve, material A, sesbania powder, sodium bicarbonate, and deionized water is 17:1.8:0.32:0.15:0.15:20;

[0037] A3. Take the material B and immerse it in an ammonium chloride solution, perform ion exchange at 75°C for 10 hours, centrifuge, wash the solid phase, and dry it to obtain material C; the ratio of the material B to the ammonium chloride solution is 1g:20mL; the concentration of the ammonium chloride solution is 1mol / L;

[0038] A4. Material C, polydienylpropylenedimethylammonium chloride, and deionized water were mixed, stirred for 1 hour, centrifuged, and the solid phase was added to the treatment solution. The mixture was ultrasonically treated for 30 minutes, and tetraethyl orthosilicate was added. The mixture was stirred for 15 hours, filtered, and the solid phase was washed, dried, ground, and calcined at 450°C for 6 hours to obtain material D. The ratio of material C, polydienylpropylenedimethylammonium chloride, deionized water, treatment solution, and tetraethyl orthosilicate was 3 g:0.18 g:50 mL:300 mL:3.8 g. The treatment solution was prepared by mixing 500 mL of ethanol, 3 g of hexadecyltrimethylammonium bromide, and 10 g of 28% ammonia water.

[0039] A5. Mix the material D, nickel acetate, and anhydrous ethanol, ultrasonically treat for 30 minutes, stir at room temperature for 4 hours, centrifuge, wash the solid phase, vacuum dry, grind it, and load it into a quartz boat. Use a tube furnace to calcine and reduce it in a mixed atmosphere of 85% hydrogen and 15% argon. Raise the temperature to 300°C at a heating rate of 2°C / min and hold for 4 hours. After the calcination and reduction, the catalyst is obtained; the dosage ratio of the material D, nickel acetate, and anhydrous ethanol is 0.25g:35mg:20mL.

[0040] Preparation Example 2

[0041] A method for preparing a catalyst for catalyzing the hydrogenation of rosin to prepare hydrogenated rosin comprises the following steps:

[0042] A1. Mix cerium nitrate hexahydrate, deionized water, and sodium hydroxide, stir ultrasonically for 20 minutes, transfer to a hydrothermal reactor and maintain at 100°C for 25 hours, cool, centrifuge, wash the solid phase, dry, add to a sodium stearate-ethanol aqueous solution, heat and stir in a water bath at 60°C for 1.5 hours, filter, wash the solid phase, and dry to obtain material A; the mass ratio of the cerium nitrate hexahydrate, deionized water, sodium hydroxide, and sodium stearate is 2.25:65:18.3:0.5; the ethanol aqueous solution is prepared by 4 mL of ethanol and 16 mL of deionized water;

[0043] A2. Mix HY molecular sieve, material A, sesbania powder, sodium bicarbonate, and deionized water, mix them evenly, knead them three times in a twin-screw extruder, and then extrude them into strips. The template uses a 2.0 mm cylindrical template, and the mixture is dried and calcined at 500° C. for 4 h to obtain material B. The mass ratio of the HY molecular sieve, material A, sesbania powder, sodium bicarbonate, and deionized water is 21:1.95:0.39:0.19:0.19:22.

[0044] A3. Take the material B and immerse it in an ammonium chloride solution, perform ion exchange at 78°C for 15 hours, centrifuge, wash the solid phase, and dry it to obtain material C; the ratio of the material B to the ammonium chloride solution is 1g:22mL; the concentration of the ammonium chloride solution is 1mol / L;

[0045] A4. Material C, polydienylpropylenedimethylammonium chloride, and deionized water were mixed, stirred for 1.5 hours, centrifuged, and the solid phase was added to the treatment solution. The mixture was ultrasonically treated for 35 minutes, and tetraethyl orthosilicate was added. The mixture was stirred for 18 hours, filtered, and the solid phase was washed, dried, ground, and calcined at 500°C for 7 hours to obtain material D. The ratio of material C, polydienylpropylenedimethylammonium chloride, deionized water, treatment solution, and tetraethyl orthosilicate was 3.5 g:0.21 g:50 mL:350 mL:4.3 g. The treatment solution was prepared by mixing 500 mL of ethanol, 3 g of hexadecyltrimethylammonium bromide, and 10 g of 28% ammonia water.

[0046] A5. Mix the material D, nickel acetate, and anhydrous ethanol, perform ultrasonic treatment for 35 min, stir at room temperature for 4.5 h, centrifuge, wash the solid phase, vacuum dry, grind it, and load it into a quartz boat. Use a tube furnace to carry out calcination reduction in a mixed atmosphere of 85% hydrogen and 15% argon. Raise the temperature to 350°C at a heating rate of 2°C / min and hold for 5 h. After the calcination reduction, the catalyst is obtained. The dosage ratio of the material D, nickel acetate, and anhydrous ethanol is 0.30 g:45 mg:25 mL.

[0047] like Figure 1-3 As shown, the catalyst prepared in this preparation example has regular morphology and uniform particle size distribution. After being coated with mesoporous silica, the morphology of the molecular sieve is transformed into an irregular ellipsoid, and no single molecular sieve exists. A mesoporous silica shell is successfully generated on the outer surface of the molecular sieve, and there is no phase separation between the core layer and the shell layer; the water contact angle inside the molecular sieve is 88.75°, and the water contact angle of the external mesoporous silica shell is 25.13°, indicating that the prepared catalyst has good hydrophilic and lipophilic properties.

[0048] Preparation Example 3

[0049] A method for preparing a catalyst for catalyzing the hydrogenation of rosin to prepare hydrogenated rosin comprises the following steps:

[0050] A1. Mix cerium nitrate hexahydrate, deionized water, and sodium hydroxide, stir ultrasonically for 25 minutes, transfer to a hydrothermal reactor and maintain at 100°C for 30 hours, cool, centrifuge, wash the solid phase, dry, add to a sodium stearate-ethanol aqueous solution, heat and stir in a water bath at 60°C for 2 hours, filter, wash the solid phase, and dry to obtain material A; the mass ratio of the cerium nitrate hexahydrate, deionized water, sodium hydroxide, and sodium stearate is 2.35:70:18.6:0.6; the ethanol aqueous solution is prepared by 4 mL of ethanol and 16 mL of deionized water;

[0051] A2. Mix HY molecular sieve, material A, sesbania powder, sodium bicarbonate, and deionized water, mix them evenly, knead them three times in a twin-screw extruder, and then extrude them into strips. The template uses a 2.0 mm cylindrical template, and the mixture is dried and calcined at 550° C. for 5 h to obtain material B. The mass ratio of the HY molecular sieve, material A, sesbania powder, sodium bicarbonate, and deionized water is 25:2.1:0.45:0.22:0.23:25.

[0052] A3. Take the material B and immerse it in an ammonium chloride solution, perform ion exchange at 80°C for 20 hours, centrifuge, wash the solid phase, and dry it to obtain material C; the ratio of the material B to the ammonium chloride solution is 1g:25mL; the concentration of the ammonium chloride solution is 1mol / L;

[0053] A4. Material C, polydienylpropylenedimethylammonium chloride, and deionized water were mixed, stirred for 2 hours, centrifuged, and the solid phase was added to the treatment solution. The mixture was ultrasonically treated for 40 minutes, and tetraethyl orthosilicate was added. The mixture was stirred for 20 hours, filtered, and the solid phase was washed, dried, ground, and calcined at 550°C for 8 hours to obtain material D. The ratio of material C, polydienylpropylenedimethylammonium chloride, deionized water, treatment solution, and tetraethyl orthosilicate was 4g:0.24g:50mL:400mL:4.8g. The treatment solution was prepared by mixing 500mL of ethanol, 3g of hexadecyltrimethylammonium bromide, and 10g of 28% ammonia water.

[0054] A5. Mix the material D, nickel acetate, and anhydrous ethanol, ultrasonically treat for 40 minutes, stir at room temperature for 5 hours, centrifuge, wash the solid phase, vacuum dry, grind it, and load it into a quartz boat. Use a tube furnace to calcine and reduce it in an atmosphere of a mixture of 85% hydrogen and 15% argon. Raise the temperature to 400°C at a heating rate of 2°C / min and maintain it for 6 hours. After the calcination and reduction, the catalyst is obtained; the dosage ratio of the material D, nickel acetate, and anhydrous ethanol is 0.35g:55mg:30mL.

[0055] Preparation Example 4

[0056] A method for preparing a catalyst for catalyzing the hydrogenation of rosin to prepare hydrogenated rosin comprises the following steps:

[0057] A1. Mix HY molecular sieve, sesbania powder, sodium bicarbonate, and deionized water, knead them three times in a twin-screw extruder, and then extrude them into strips. The template uses a 2.0 mm cylindrical template. The material is dried and calcined at 500° C. for 4 h to obtain material B. The mass ratio of the HY molecular sieve, sesbania powder, sodium bicarbonate, and deionized water is 21:0.39:0.19:0.19:22.

[0058] A2. Take the material B and immerse it in an ammonium chloride solution, perform ion exchange at 78°C for 15 hours, centrifuge, wash the solid phase, and dry it to obtain material C; the ratio of the material B to the ammonium chloride solution is 1g:22mL; the concentration of the ammonium chloride solution is 1mol / L;

[0059] A3. Mix the material C, polydienylpropylenedimethylammonium chloride, and deionized water, stir for 1.5 hours, centrifuge, take the solid phase and add it to the treatment solution, ultrasonicate for 35 minutes, add tetraethyl orthosilicate, stir for 18 hours, filter, wash the solid phase, dry, grind, and calcine at 500°C for 7 hours to obtain material D; the ratio of the material C, polydienylpropylenedimethylammonium chloride, deionized water, treatment solution, and tetraethyl orthosilicate is 3.5g:0.21g:50mL:350mL:4.3g; the treatment solution is prepared by mixing 500mL of ethanol, 3g of hexadecyltrimethylammonium bromide, and 10g of 28% ammonia water;

[0060] A4. Mix the material D, nickel acetate, and anhydrous ethanol, ultrasonically treat for 35 minutes, stir at room temperature for 4.5 hours, centrifuge, wash the solid phase, vacuum dry, grind it, and load it into a quartz boat. Use a tube furnace to calcine and reduce it in an atmosphere of a mixture of 85% hydrogen and 15% argon. Raise the temperature to 350°C at a heating rate of 2°C / min and hold for 5 hours. After the calcination and reduction, the catalyst is obtained; the dosage ratio of the material D, nickel acetate, and anhydrous ethanol is 0.30 g:45 mg:25 mL.

[0061] Preparation Example 5

[0062] A method for preparing a catalyst for catalyzing the hydrogenation of rosin to prepare hydrogenated rosin comprises the following steps:

[0063] A1. Mix cerium nitrate hexahydrate, deionized water, and sodium hydroxide, stir ultrasonically for 20 minutes, transfer to a hydrothermal reactor and maintain at 100°C for 25 hours, cool, centrifuge, wash the solid phase, dry, add to a sodium stearate-ethanol aqueous solution, heat and stir in a water bath at 60°C for 1.5 hours, filter, wash the solid phase, and dry to obtain material A; the mass ratio of the cerium nitrate hexahydrate, deionized water, sodium hydroxide, and sodium stearate is 2.25:65:18.3:0.5; the ethanol aqueous solution is prepared by 4 mL of ethanol and 16 mL of deionized water;

[0064] A2. Mix HY molecular sieve, material A, sesbania powder, sodium bicarbonate, and deionized water, mix them evenly, knead them three times in a twin-screw extruder, and then extrude them into strips. The template uses a 2.0 mm cylindrical template, and the mixture is dried and calcined at 500° C. for 4 h to obtain material B. The mass ratio of the HY molecular sieve, material A, sesbania powder, sodium bicarbonate, and deionized water is 21:1.95:0.39:0.19:0.19:22.

[0065] A3. Take the material B, nickel acetate, and anhydrous ethanol, mix them, ultrasonically treat for 35 minutes, stir at room temperature for 4.5 hours, centrifuge, wash the solid phase, vacuum dry it, grind it and put it into a quartz boat, use a tube furnace to calcine and reduce it in a mixed gas atmosphere of 85% hydrogen and 15% argon, and heat it to 350°C at a heating rate of 2°C / min and hold it for 5 hours. After the calcination and reduction, the catalyst is obtained; the dosage ratio of the material B, nickel acetate, and anhydrous ethanol is 0.30g:45mg:25mL.

[0066] Example 1

[0067] A method for preparing a hydrogenated rosin derivative comprises the following steps:

[0068] S1. Mix rosin (purchased from Shanghai Titan Technology Co., Ltd.), methyl oleate, and deionized water, stir and dissolve at 90° C., place in an autoclave, add the catalyst prepared in Preparation Example 1, seal, check for leaks, replace with nitrogen and hydrogen three times each, raise the temperature to 150° C., add a hydrogen pressure of 5 MPa, and mechanically stir at a speed of 500 r / min to react for 2 h. Cool, take the product, let it stand and separate, and take the upper oil phase to obtain hydrogenated rosin; the mass ratio of the rosin, methyl oleate, deionized water, and catalyst is 1:10:10:0.001; the conversion rate of hydrogenated rosin obtained by hydrogenation of rosin is 99.82%.

[0069] S2. The hydrogenated rosin was crushed and mixed with glycidyl methacrylate, p-hydroxyanisole and triethylamine in a nitrogen atmosphere, and the mixture was heated to 88° C. with stirring, and the mixture was kept warm for 2 hours. The mixture was heated to 120° C. and kept warm for 4 hours to obtain a hydrogenated rosin-based acrylate derivative; the mass ratio of the hydrogenated rosin, glycidyl methacrylate, p-hydroxyanisole and triethylamine was 38:16:0.045:0.065.

[0070] Example 2

[0071] A method for preparing a hydrogenated rosin derivative comprises the following steps:

[0072] S1. Mix rosin, methyl oleate, and deionized water, stir and dissolve at 90° C., place in an autoclave, add the catalyst prepared in Preparation Example 2, seal, check for leaks, replace with nitrogen and hydrogen three times each, raise the temperature to 150° C., add hydrogen at a pressure of 5 MPa, mechanically stir at a speed of 500 r / min for 2 hours, cool, take the product, let it stand and separate, and take the upper oil phase to obtain hydrogenated rosin; the mass ratio of the rosin, methyl oleate, deionized water, and catalyst is 1:10:10:0.001; the conversion rate of hydrogenated rosin obtained by hydrogenation of rosin is 99.86%.

[0073] S2. The hydrogenated rosin was crushed and mixed with glycidyl methacrylate, p-hydroxyanisole and triethylamine in a nitrogen atmosphere, and the mixture was heated to 88° C. with stirring, and the mixture was kept warm for 2 hours. The mixture was heated to 120° C. and kept warm for 4 hours to obtain a hydrogenated rosin-based acrylate derivative; the mass ratio of the hydrogenated rosin, glycidyl methacrylate, p-hydroxyanisole and triethylamine was 38:16:0.045:0.065.

[0074] Example 3

[0075] A method for preparing a hydrogenated rosin derivative comprises the following steps:

[0076] S1. Mix rosin (purchased from Shanghai Titan Technology Co., Ltd.), methyl oleate, and deionized water, stir and dissolve at 90° C., place in an autoclave, add the catalyst prepared in Preparation Example 3, seal, check for leaks, replace with nitrogen and hydrogen three times each, heat to 150° C., add hydrogen at a pressure of 5 MPa, and mechanically stir at a speed of 500 r / min to react for 2 h. Cool, take the product, let it stand and separate, and take the upper oil phase to obtain hydrogenated rosin; the mass ratio of rosin, methyl oleate, deionized water, and catalyst is 1:10:10:0.001; the conversion rate of hydrogenated rosin obtained by hydrogenation of rosin is 99.83%.

[0077] S2. The hydrogenated rosin was crushed and mixed with glycidyl methacrylate, p-hydroxyanisole and triethylamine in a nitrogen atmosphere, and the mixture was heated to 88° C. with stirring, and the mixture was kept warm for 2 hours. The mixture was heated to 120° C. and kept warm for 4 hours to obtain a hydrogenated rosin-based acrylate derivative; the mass ratio of the hydrogenated rosin, glycidyl methacrylate, p-hydroxyanisole and triethylamine was 38:16:0.045:0.065.

[0078] Example 4

[0079] A method for preparing a hydrogenated rosin derivative comprises the following steps:

[0080] S1. Mix rosin (purchased from Shanghai Titan Technology Co., Ltd.), methyl oleate, and deionized water, stir and dissolve at 90° C., place in an autoclave, add the catalyst prepared in Preparation Example 4, seal, check for leaks, replace with nitrogen and hydrogen three times each, raise the temperature to 150° C., add hydrogen at a pressure of 5 MPa, and mechanically stir at a speed of 500 r / min to react for 2 h. Cool, take the product, let it stand and separate, and take the upper oil phase to obtain hydrogenated rosin; the mass ratio of the rosin, methyl oleate, deionized water, and catalyst is 1:10:10:0.001; the conversion rate of hydrogenated rosin obtained by hydrogenation of rosin is 83.37%.

[0081] S2. The hydrogenated rosin was crushed and mixed with glycidyl methacrylate, p-hydroxyanisole and triethylamine in a nitrogen atmosphere, and the mixture was heated to 88° C. with stirring, and the mixture was kept warm for 2 hours. The mixture was heated to 120° C. and kept warm for 4 hours to obtain a hydrogenated rosin-based acrylate derivative; the mass ratio of the hydrogenated rosin, glycidyl methacrylate, p-hydroxyanisole and triethylamine was 38:16:0.045:0.065.

[0082] Example 5

[0083] A method for preparing a hydrogenated rosin derivative comprises the following steps:

[0084] S1. Mix rosin (purchased from Shanghai Titan Technology Co., Ltd.), methyl oleate, and deionized water, stir and dissolve at 90° C., place in an autoclave, add the catalyst prepared in Preparation Example 5, seal, check for leaks, replace with nitrogen and hydrogen three times each, raise the temperature to 150° C., add a hydrogen pressure of 5 MPa, and mechanically stir at a speed of 500 r / min to react for 2 h. Cool, take the product, let it stand and separate, and take the upper oil phase to obtain hydrogenated rosin; the mass ratio of the rosin, methyl oleate, deionized water, and catalyst is 1:10:10:0.001; the conversion rate of hydrogenated rosin obtained by hydrogenation of rosin is 67.37%.

[0085] S2. The hydrogenated rosin was crushed and mixed with glycidyl methacrylate, p-hydroxyanisole and triethylamine in a nitrogen atmosphere, and the mixture was heated to 88° C. with stirring, and the mixture was kept warm for 2 hours. The mixture was heated to 120° C. and kept warm for 4 hours to obtain a hydrogenated rosin-based acrylate derivative; the mass ratio of the hydrogenated rosin, glycidyl methacrylate, p-hydroxyanisole and triethylamine was 38:16:0.045:0.065.

[0086] Application Example 1

[0087] 40 g of the hydrogenated rosin-based acrylate derivative prepared in Example 2 was compounded with 40 g of hydroxypropyl methacrylate, 40 g of cyclotrimethylolpropane formal acrylate, 0.2 g of p-hydroxyanisole, 4 g of IRGACURE 907, 1 g of TEGO-450 leveling agent, and 1 g of BYK-057 to prepare a light-curing coating.

[0088] Application Example 2

[0089] 60 g of hydroxypropyl methacrylate, 60 g of cyclotrimethylolpropane formal acrylate, 0.2 g of p-hydroxyanisole, 4 g of IRGACURE 907, 1 g of TEGO-450 leveling agent, and 1 g of BYK-057 were compounded to prepare a light-curing coating.

[0090] Performance Testing

[0091] The light-curing coatings prepared in Example 1 and Example 2 were sprayed onto PVC substrates respectively, with the film thickness controlled to be about 20 μm. The coatings were leveled in a 60°C oven for 5 minutes, and then irradiated with an energy of 500 mJ / cm 2 The films were cured under ultraviolet light and placed at room temperature for 24 hours before performance tests. The hardness was tested in accordance with the standard GB / T 6739-2006; the adhesion was tested in accordance with the standard GB / T 5210-2006; and the abrasion resistance was tested in accordance with the standard ASTM F2357-04. The test results are shown in Table 1 below.

[0092] Table 1

[0093] hardness Adhesion / MPa RCA wear times Application Example 1 5H 3.69 3900 Application Example 2 4H 3.12 3700

[0094] As can be seen from Table 1, the coating prepared using the hydrogenated rosin-based acrylate derivative prepared in the present application as a coating monomer has good hardness, bonding strength and wear resistance.

[0095] The above describes some embodiments of the present invention in detail, but the contents described are only preferred embodiments of the present invention and should not be considered to limit the scope of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.

Claims

1. A method for preparing a hydrogenated rosin derivative, characterized in that: The preparation method of the hydrogenated rosin derivative comprises the following steps: S1, taking a rosin solution and performing a hydrogenation reaction under the catalytic action of a catalyst to obtain hydrogenated rosin; S2, crushing the hydrogenated rosin, mixing it with glycidyl methacrylate, p-hydroxyanisole and triethylamine in a nitrogen atmosphere, and reacting at room temperature to obtain the hydrogenated rosin derivative; The catalyst comprises a nickel-based active component and a hydrophilic and lipophilic carrier; The hydrophilic and lipophilic carrier comprises a hydrophilic mesoporous silica shell layer and an lipophilic molecular sieve core cavity.

2. The method for preparing a hydrogenated rosin derivative according to claim 1, characterized in that: The preparation method of the catalyst comprises the following steps: A1. Mix cerium nitrate hexahydrate, deionized water, and sodium hydroxide, stir ultrasonically, perform hydrothermal treatment, cool, and centrifuge. Wash the solid phase, dry it, and add it to a sodium stearate-ethanol aqueous solution. Heat and stir in a water bath, filter, wash the solid phase, and dry it to obtain material A. A2. Mix HY molecular sieve, material A, sesbania powder, sodium bicarbonate, and deionized water, extrude into strips, dry, and calcine to obtain material B. A3, taking the material B and immersing it in an ammonium chloride solution, performing ion exchange, centrifuging, washing the solid phase, and drying to obtain material C; A4. Mix material C, polydiallylpropylenedimethylammonium chloride, and deionized water, centrifuge, add the solid phase to the treatment solution, ultrasonicate, add tetraethyl orthosilicate, stir, filter, wash the solid phase, dry, grind, and calcine to obtain material D. A5. Take the material D, nickel acetate, and anhydrous ethanol, mix them, ultrasonicate them, stir them, centrifuge them, wash the solid phase, vacuum dry them, grind them, and calcine them to obtain the catalyst.

3. The method for preparing a hydrogenated rosin derivative according to claim 1, wherein: In step S1, the mass ratio of the rosin solution to the catalyst is 21-22:0.001-0.

002.

4. The method for preparing a hydrogenated rosin derivative according to claim 1, wherein: In step S2, the mass ratio of hydrogenated rosin, glycidyl methacrylate, p-hydroxyanisole, and triethylamine is 35-40:15-17:0.04-0.05:0.06-0.

07.

5. The method for preparing a hydrogenated rosin derivative according to claim 1, characterized in that: In step A1, the mass ratio of the cerium nitrate hexahydrate, deionized water, sodium hydroxide, and sodium stearate is 2.14-2.35:60-70:17.9-18.6:0.4-0.6; and the ethanol aqueous solution is prepared from 4 mL of ethanol and 16 mL of deionized water.

6. The method for preparing a hydrogenated rosin derivative according to claim 1, wherein: In step A2, the mass ratio of the HY molecular sieve, material A, sesbania powder, sodium bicarbonate, and deionized water is 17-25:1.8-2.1:0.32-0.45:0.15-0.22:0.15-0.23:20-25.

7. The method for preparing a hydrogenated rosin derivative according to claim 1, wherein: In step A3, the ratio of material B to ammonium chloride solution is 1 g: 20-25 mL; the concentration of the ammonium chloride solution is 1 mol / L.

8. The method for preparing a hydrogenated rosin derivative according to claim 1, wherein: In step A4, the ratio of material C, polydialkylpropylenedimethylammonium chloride, deionized water, treatment liquid, and ethyl orthosilicate is 3-4 g: 0.18-0.24 g: 50 mL: 300-400 mL: 3.8-4.8 g; the treatment liquid is prepared by mixing 500 mL of ethanol, 3 g of hexadecyltrimethylammonium bromide, and 10 g of 28% ammonia water.

9. The method for preparing a hydrogenated rosin derivative according to claim 1, wherein: In step A5, the dosage ratio of the material D, nickel acetate, and anhydrous ethanol is 0.25-0.35 g: 35-55 mg: 20-30 mL.

Images