A process for the preparation of a hydrogenated rosin derivative

Abstract

The application discloses a preparation method of a hydrogenated rosin derivative and belongs to the technical field of rosin derivative preparation. The method comprises the following steps: taking a rosin solution and performing hydrogenation reaction under the catalysis of a catalyst to obtain hydrogenated rosin; taking the hydrogenated rosin, crushing and treating, mixing with glycidyl methacrylate, p-hydroxyanisole and triethylamine in a nitrogen atmosphere, and performing heat preservation reaction to obtain the hydrogenated rosin derivative; the catalyst comprises a nickel-based active component and a hydrophilic-lipophilic carrier; the hydrophilic-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 the hydrophilic-lipophilic catalyst; and the coating prepared by using the hydrogenated rosin-based acrylate derivative prepared from the hydrogenated rosin as a coating monomer has good hardness, bonding strength and wear resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of rosin derivative preparation, and particularly relates to a preparation method of hydrogenated rosin derivative. BACKGROUND

[0002] Rosin is a natural resin with significant thermoplastic properties. The chemical composition of rosin is mainly composed of resin acids, in addition to some fatty acids and neutral substances. These components work together to make rosin and its various derivatives have very wide applications in industrial and commercial fields.

[0003] Due to the presence of unsaturated conjugated double bonds in the molecular structure of rosin, they have high sensitivity to oxygen. When rosin is exposed to an environment containing oxygen, it is very easy to undergo oxidation reaction. This oxidation will cause the performance of rosin materials to gradually decline, affecting its use value. Therefore, in order to improve the practicality and stability of rosin, researchers and engineers have developed various modification technologies, including isomerization, disproportionation, hydrogenation, maleation and esterification methods. After processing by these methods, the derivatives of rosin not only maintain the original properties, but also increase new functions, thereby showing more excellent performance in different application occasions. Among its derivative products, hydrogenated rosin is an important modified material, which can be prepared by hydrogenation reaction. Hydrogenated rosin has good antioxidant properties, low brittleness and high thermal stability, and is non-toxic, so it has a very wide range of applications in industry, such as adhesives, synthetic rubber, paint, ink and the like.

[0004] The catalysts with noble metal as active component have made good progress in the hydrogenation of rosin, but the noble metal also has some inevitable shortcomings, such as high price, relatively limited availability and instability, which greatly increases the cost of its application in industrial production. In order to improve this problem, researchers begin to focus on the development of non-noble metal catalysts, and nickel-based catalysts are the most widely used among them, which can provide reliable guarantee for the catalytic cracking hydrogenation of rosin. For the purpose of protecting the ecological environment, people pay more and more attention to the development of green chemistry and environmentally friendly chemistry. Because the residual solvents after various chemical reactions can cause more or less harm to the ecological environment and human health, it is particularly important to follow the requirements of green chemistry, such as the reuse of catalysts and the use of green solvents. The solvent can play a certain auxiliary role in the interaction between the carrier and the metal and in the adsorption and desorption steps, so it can affect the selectivity and activity of the reaction, which can be attributed to the geometry and polarity of the solvent. Researchers have tried to use 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 various air pollutants. Water has the advantages of abundance and low cost, and it is easy to obtain and separate from the reaction mixture. In many cases, water as a solvent can not only accelerate the rate of organic reaction to some extent, but also improve the regional selectivity of chemical reaction. Due to the hydrophobicity of rosin hydrogenation catalyst, it has poor solubility or miscibility with water, which leads to low yield. Therefore, how to improve the miscibility of rosin hydrogenation catalyst in water has become an important research direction. SUMMARY

[0005] The purpose of the present application is to provide a preparation method of hydrogenated rosin derivatives, which solves 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 application can be realized by the following technical solutions.

[0007] A preparation method of hydrogenated rosin derivatives, the preparation method of hydrogenated rosin derivatives comprises the following steps:

[0008] S1, taking rosin solution to carry out hydrogenation reaction under the catalysis of catalyst to obtain hydrogenated rosin;

[0009] S2, taking the hydrogenated rosin to carry out crushing treatment, mixing with glycidyl methacrylate, p-hydroxyanisole and triethylamine in a nitrogen atmosphere, and carrying out heat preservation reaction to obtain the hydrogenated rosin derivatives;

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

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

[0012] As a further scheme of the present application, the preparation method of the catalyst comprises the following steps:

[0013] A1, mix cerium nitrate hexahydrate, deionized water and sodium hydroxide, ultrasonic stirring, hydrothermal treatment, cooling, centrifugal separation, take the solid phase washing, drying, adding to the sodium stearate-ethanol aqueous solution, water bath heating stirring, filtration, taking the solid phase washing, drying to obtain material A; the rod-like cerium oxide is prepared by hydrothermal synthesis method, then the rod-like cerium oxide is modified by sodium stearate to improve the particle size dispersibility and stability, and the rod-like cerium oxide with lipophilicity is obtained;

[0014] A2, mix HY type molecular sieve, material A, sesbania powder, sodium bicarbonate and deionized water uniformly, extrude into strips, dry and bake to obtain material B; the lipophilic rod-like cerium oxide is co-sintered with the molecular sieve, so that the molecular sieve cavity is endowed with good lipophilic property, and the rod-like cerium oxide is introduced, which acts as an anchoring site for loading nickel active components on one hand, and promotes electron migration by doping cerium on the other hand, thereby improving the catalytic efficiency;

[0015] A3, immerse the material B in an ammonium chloride solution, perform ammonium ion exchange, centrifugal separation, take the solid phase washing, drying, to obtain material C;

[0016] A4, mix the material C, polydiallyl dimethyl ammonium chloride and deionized water for surface modification, centrifugal separation, take the solid phase and add to a treatment liquid, ultrasonic treatment, add tetraethyl orthosilicate, stirring, filtration, take the solid phase washing, drying, grinding, baking to obtain material D with a mesoporous silica coated molecular sieve structure;

[0017] A5, mix the material D, nickel acetate and anhydrous ethanol, ultrasonic treatment, stirring, centrifugal separation, take the solid phase washing, vacuum drying, grinding, calcination reduction, to obtain a hydrophilic-lipophilic catalyst loaded with active nickel.

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

[0019] As a further scheme of the present application, in step S2, the mass ratio of the 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 scheme of the present application, 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; the aqueous ethanol solution is prepared from 4 mL of ethanol and 16 mL of deionized water.

[0021] As a further scheme of the present application, in step A2, the mass ratio of the HY type molecular sieve, the material A, the sesbania gum, the sodium bicarbonate, and the 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 scheme of the present application, in step A3, the ratio of the material B and the ammonium chloride solution is 1 g:20-25 mL; the concentration of the ammonium chloride solution is 1 mol / L.

[0023] As a further scheme of the present application, in step A4, the ratio of the material C, the poly dialkyl propyldimethyl ammonium chloride, the deionized water, the treatment liquid, and the tetraethyl 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 cetyltrimethylammonium bromide, and 10 g of 28% ammonia water.

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

[0025] The present application has the following beneficial effects:

[0026] The present application discloses a preparation method of a hydrogenated rosin derivative. The preparation method of the hydrophilic-lipophilic catalyst is provided. The lipophilic molecular sieve is used as a core layer, and the surface is coated with hydrophilic mesoporous silica. The pores of the core layer and the shell layer have good connectivity, small particle size, and the generation of shell mesopores effectively enhances the mass transfer performance of the catalytic reaction, and improves the yield of hydrogenated rosin. In addition, the water-oil blend liquid is used as a solvent for rosin, which is more environmentally friendly.

[0027] Further, the hydrogenated rosin-based acrylate derivative monomer is prepared by using hydrogenated rosin, a triphenyl ring skeleton structure is introduced, and the hardness, bonding strength, and wear resistance of the prepared coating are improved. BRIEF DESCRIPTION OF DRAWINGS

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

[0029] Figure 1 FIG. 2 is a SEM image of the catalyst prepared in Preparation Example 2 of the present application.

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

[0031] Figure 3 is a water droplet contact angle diagram of the catalyst prepared in Preparation Example 2 of the present application. DETAILED DESCRIPTION

[0032] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative labor fall within the protection scope of the present application.

[0033] Preparation Example 1

[0034] A preparation method of a catalyst for catalytically preparing hydrogenated rosin from rosin, comprising the following steps:

[0035] A1, mix cerium nitrate hexahydrate, deionized water and sodium hydroxide, ultrasonic stirring for 15 min, transfer to a hydrothermal reaction kettle, keep at 100℃ for 20h, cool, centrifugal separation, take the solid phase, wash, dry, add to a sodium stearate-ethanol aqueous solution, heat stirring at 60℃ water bath for 1h, filter, take the solid phase, wash, 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 4mL ethanol and 16mL deionized water;

[0036] A2, mix HY type molecular sieve (silicon aluminum ratio = 5, purchased from Guangdong Yunxing Biotechnology Co., Ltd.), material A, sesbania powder, sodium bicarbonate and deionized water uniformly, extrude into strips after mixing and kneading 3 times in a double screw extruder, use 2.0mm cylindrical template as a template, dry, calcine at 450℃ for 3h 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, immerse the material B in an ammonium chloride solution, ion exchange at 75℃ for 10h, centrifugal separation, take the solid phase, wash, dry to obtain material C; the proportioning ratio of the material B and the ammonium chloride solution is 1g:20mL; the concentration of the ammonium chloride solution is 1mol / L;

[0038] A4, the material C, polydialkyl dimethyl ammonium chloride, deionized water were mixed, stirred for 1 h, centrifuged, the solid phase was added to the treatment liquid, ultrasonic treatment for 30 min, and tetraethyl orthosilicate was added, stirred for 15 h, filtered, the solid phase was washed, dried, ground, and calcined at 450℃ for 6 h to obtain the material D; the amount ratio of the material C, polydialkyl dimethyl ammonium chloride, deionized water, the treatment liquid, and tetraethyl orthosilicate was 3g: 0.18g: 50mL: 300mL: 3.8g; the treatment liquid was prepared by mixing 500mL of ethanol, 3g of cetyltrimethylammonium bromide, and 10g of 28% ammonia water;

[0039] A5, the material D, nickel acetate, and anhydrous ethanol were mixed, ultrasonic treatment for 30 min, stirred at room temperature for 4 h, centrifuged, the solid phase was washed, vacuum dried, ground, and loaded into a quartz boat, and calcination reduction was carried out in a tube furnace under the atmosphere of a mixed gas of 85% hydrogen and 15% argon, the temperature was raised to 300℃ at a rate of 2℃ / min and maintained for 4 h, and the catalyst was obtained after the calcination reduction; the amount ratio of the material D, nickel acetate, and anhydrous ethanol was 0.25g: 35mg: 20mL.

[0040] Preparation Example 2

[0041] A preparation method of a catalyst for catalyzing hydrogenation of rosin to prepare hydrogenated rosin, comprising the following steps:

[0042] A1, cerium nitrate hexahydrate, deionized water, and sodium hydroxide were mixed, ultrasonic stirring for 20 min, transferred to a hydrothermal reaction kettle, kept at 100℃ for 25 h, cooled, centrifuged, the solid phase was washed, dried, added to a sodium stearate-ethanol aqueous solution, heated and stirred at 60℃ for 1.5 h, filtered, the solid phase was washed, dried to obtain the material A; the mass ratio of the cerium nitrate hexahydrate, deionized water, sodium hydroxide, and sodium stearate was 2.25: 65: 18.3: 0.5; the ethanol aqueous solution was prepared by 4mL of ethanol and 16mL of deionized water;

[0043] A2, the HY type molecular sieve, the material A, the sesbania powder, sodium bicarbonate, and deionized water were mixed uniformly, extruded into strips in a double screw extruder after kneading three times, the template adopted a 2.0mm cylindrical template, dried, and calcined at 500℃ for 4 h to obtain the material B; the mass ratio of the HY type molecular sieve, the material A, the sesbania powder, sodium bicarbonate, and deionized water was 21: 1.95: 0.39: 0.19: 0.19: 22;

[0044] A3, taking the material B to be immersed in an ammonium chloride solution, ion exchange at 78℃ for 15h, centrifugal separation, taking the solid phase to be washed, dried, to obtain material C; the matching ratio of the material B and the ammonium chloride solution is 1g:22mL; the concentration of the ammonium chloride solution is 1mol / L;

[0045] A4, taking the material C, polydiene-based propyldimethylammonium chloride, deionized water to be mixed, stirring for 1.5h, centrifugal separation, taking the solid phase to be added to a treatment liquid, ultrasonic treatment for 35min, adding tetraethyl orthosilicate, stirring for 18h, filtering, taking the solid phase to be washed, dried, ground, calcining at 500℃ for 7h, to obtain material D; the matching ratio of the material C, polydiene-based propyldimethylammonium chloride, deionized water, the treatment liquid, tetraethyl orthosilicate is 3.5g:0.21g:50mL:350mL:4.3g; the treatment liquid is configured by mixing 500mL of ethanol, 3g of cetyltrimethylammonium bromide and 10g of 28% ammonia water;

[0046] A5, taking the material D, nickel acetate, anhydrous ethanol to be mixed, ultrasonic treatment for 35min, stirring at room temperature for 4.5h, centrifugal separation, taking the solid phase to be washed, vacuum drying, grinding and loading into a quartz boat, using a tube furnace to carry out calcination reduction under the atmosphere of a mixed gas of 85% hydrogen and 15% argon, with the temperature rising rate of 2℃ / min, the temperature rising to 350℃ and keeping for 5h, to obtain the catalyst after the calcination reduction is completed; the matching ratio of the material D, nickel acetate, anhydrous ethanol is 0.30g:45mg:25mL.

[0047] As shown in Figures 1-3 The catalyst prepared in the present preparation example has regular morphology and uniform particle size distribution, after the mesoporous silica coating treatment, the morphology of the molecular sieve is changed into irregular ellipsoidal shape, and there is no single molecular sieve, the outer surface of the molecular sieve successfully generates a mesoporous silica shell layer, and there is no phase separation phenomenon between the core layer and the shell layer; the internal water contact angle of the molecular sieve is 88.75°, and the water contact angle of the external mesoporous silica shell layer is 25.13°, indicating that the prepared catalyst has good hydrophilic and lipophilic performance.

[0048] Preparation Example 3

[0049] A preparation method of a catalyst for catalyzing the hydrogenation of rosin to prepare hydrogenated rosin, comprising the following steps:

[0050] A1, cerium nitrate hexahydrate, deionized water, sodium hydroxide are mixed and ultrasonic stirring is carried out for 25 min, then the mixture is transferred into a hydrothermal reaction kettle and kept at 100℃ for 30 h, then the mixture is cooled, centrifuged, and the solid phase is washed and dried, and then the solid phase is added into a sodium stearate-ethanol aqueous solution, heated and stirred at 60℃ for 2 h, filtered, and the solid phase is washed and dried 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 mixing 4 mL of ethanol and 16 mL of deionized water;

[0051] A2, the HY type molecular sieve, material A, sesbania powder, sodium bicarbonate and deionized water are uniformly mixed, then the mixture is kneaded in a double screw extruder for 3 times and then extruded into a strip shape, a 2.0 mm cylindrical mold plate is used for drying and calcination at 550℃ for 5 h to obtain material B; the mass ratio of the HY type molecular sieve, material A, sesbania powder, sodium bicarbonate and deionized water is 25:2.1:0.45:0.22:0.23:25;

[0052] A3, the material B is immersed in an ammonium chloride solution and ion exchanged at 80℃ for 20 h, then the mixture is centrifuged, the solid phase is washed and dried to obtain material C; the ratio of the material B and the ammonium chloride solution is 1 g:25 mL; the concentration of the ammonium chloride solution is 1 mol / L;

[0053] A4, the material C, poly dialkyl dimethyl ammonium chloride and deionized water are mixed and stirred for 2 h, then the mixture is centrifuged, the solid phase is added into a treatment liquid, ultrasonic treated for 40 min, then tetraethyl orthosilicate is added and stirred for 20 h, then the mixture is filtered, the solid phase is washed and dried, ground and calcined at 550℃ for 8 h to obtain material D; the ratio of the material C, poly dialkyl dimethyl ammonium chloride, deionized water, treatment liquid and tetraethyl orthosilicate is 4 g:0.24 g:50 mL:400 mL:4.8 g; the treatment liquid is prepared by mixing 500 mL of ethanol, 3 g of cetyltrimethylammonium bromide and 10 g of 28% ammonia water;

[0054] A5, the material D, nickel acetate and anhydrous ethanol are mixed, ultrasonic treated for 40 min, stirred at room temperature for 5 h, then the mixture is centrifuged, the solid phase is washed and vacuum dried, then the solid phase is ground and loaded into a quartz boat, and a tube furnace is used for calcination reduction in a mixed gas atmosphere of 85% hydrogen and 15% argon, the temperature is raised to 400℃ at a rate of 2℃ / min and kept for 6 h, and the catalyst is obtained after the calcination reduction is completed; the ratio of the material D, nickel acetate and anhydrous ethanol is 0.35 g:55 mg:30 mL.

[0055] Preparation Example 4

[0056] A preparation method of a catalyst for preparing hydrogenated rosin by catalytic hydrogenation of rosin, comprising the following steps:

[0057] A1, HY type molecular sieve, sesbania powder, sodium bicarbonate, deionized water are uniformly mixed, and then extruded into strips after three times of kneading in a double screw extruder, a 2.0 mm cylindrical template is used for molding, drying, and calcining at 500 DEG C for 4h to obtain material B; the mass ratio of the HY type molecular sieve, sesbania powder, sodium bicarbonate, deionized water is 21:0.39:0.19:0.19:22;

[0058] A2, the material B is immersed in an ammonium chloride solution, ion exchanged at 78 DEG C for 15h, centrifuged, the solid phase is washed, dried, and material C is obtained; the amount ratio of the material B and the ammonium chloride solution is 1g:22mL; the concentration of the ammonium chloride solution is 1mol / L;

[0059] A3, the material C, polydialkylammonium chloride, deionized water are mixed, stirred for 1.5h, centrifuged, the solid phase is added to a treatment liquid, ultrasonic treated for 35min, tetraethyl orthosilicate is added, stirred for 18h, filtered, the solid phase is washed, dried, ground, calcined at 500 DEG C for 7h to obtain material D; the amount ratio of the material C, polydialkylammonium chloride, deionized water, treatment liquid, tetraethyl orthosilicate is 3.5g:0.21g:50mL:350mL:4.3g; the treatment liquid is prepared by mixing 500mL of ethanol, 3g of cetyltrimethylammonium bromide and 10g of 28% ammonia water;

[0060] A4, the material D, nickel acetate, anhydrous ethanol are mixed, ultrasonic treated for 35min, stirred at room temperature for 4.5h, centrifuged, the solid phase is washed, vacuum dried, ground and loaded into a quartz boat, and calcination reduction is carried out in a tube furnace under the atmosphere of a mixture of 85% hydrogen and 15% argon, the temperature is raised to 350 DEG C at a rate of 2 DEG C / min and kept for 5h, and the catalyst is obtained after the calcination reduction; the amount ratio of the material D, nickel acetate, anhydrous ethanol is 0.30g:45mg:25mL.

[0061] Preparation example 5

[0062] A preparation method of a catalyst for preparing hydrogenated rosin by catalytic hydrogenation of rosin, comprising the following steps:

[0063] A1, the cerium nitrate hexahydrate, deionized water, sodium hydroxide are mixed, and ultrasonic stirring is performed for 20 min, and then the mixture is transferred to a hydrothermal reaction kettle and kept at 100℃ for 25 h. After cooling, centrifugal separation is performed, and the solid phase is washed and dried. The solid phase is added to a sodium stearate-ethanol aqueous solution, and stirring is performed in a 60℃ water bath for 1.5 h. Filtration is performed, and the solid phase is washed and dried 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 mixing 4 mL of ethanol and 16 mL of deionized water.

[0064] A2, the HY type molecular sieve, material A, sesbania powder, sodium bicarbonate, and deionized water are uniformly mixed, and then kneaded in a double-screw extruder for 3 times and then extruded into a strip shape. A 2.0 mm cylindrical mold plate is used for drying and calcination at 500℃ for 4 h to obtain material B. The mass ratio of the HY type molecular sieve, material A, sesbania powder, sodium bicarbonate, and deionized water is 21:1.95:0.39:0.19:0.19:22.

[0065] A3, the material B, nickel acetate, and anhydrous ethanol are mixed, and ultrasonic treatment is performed for 35 min. Stirring is performed at room temperature for 4.5 h, and then centrifugal separation is performed. The solid phase is washed and vacuum dried. After grinding, the solid phase is loaded into a quartz boat, and calcination reduction is performed in a tube furnace in a mixed gas atmosphere of 85% hydrogen and 15% argon. The temperature is increased to 350℃ at a rate of 2℃ / min and maintained for 5 h. After the calcination reduction is completed, the catalyst is obtained. The amount ratio of the material B, nickel acetate, and anhydrous ethanol is 0.30 g:45 mg:25 mL.

[0066] Example 1

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

[0068] S1, rosin (purchased from Shanghai Titan Science and Technology Co., Ltd.), methyl oleate, and deionized water are mixed and stirred to dissolve at 90℃. The mixture is placed in a high-pressure reaction kettle, and the catalyst prepared in Preparation Example 1 is added. After sealing and leak detection, the reaction kettle is replaced with nitrogen and hydrogen for 3 times each. The temperature is increased to 150℃, and mechanical stirring is performed at a speed of 500 r / min under a hydrogen pressure of 5 MPa for 2 h. After cooling, the product is allowed to stand and separate into layers, and the upper oil phase is taken 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 rosin to hydrogenated rosin is 99.82%.

[0069] S2, take the hydrogenated rosin crushing treatment, mixed with glycidyl methacrylate, p-hydroxyanisole and triethylamine in a nitrogen atmosphere, stirring to 88℃, incubation reaction 2 hours, heating to 120℃, incubation reaction 4 hours, to get hydrogenated rosin acrylate derivative; the mass ratio of hydrogenated rosin, glycidyl methacrylate, p-hydroxyanisole, triethylamine is 38:16:0.045:0.065.

[0070] Example 2

[0071] A preparation method of hydrogenated rosin derivative, comprising the following steps:

[0072] S1, take rosin, methyl oleate and deionized water mixed, stirring to dissolve at 90℃, placed in high pressure reactor, adding the catalyst prepared in preparation example 2, sealed, leak detection, with nitrogen and hydrogen each replacement 3 times, heating to 150℃, hydrogen pressure 5MPa, with 500r / min mechanical stirring reaction 2h, cooling, take the product to stand stratification, take the upper oil phase to get hydrogenated rosin; the mass ratio of rosin, methyl oleate, deionized water, catalyst is 1:10:10:0.001; the conversion rate of rosin hydrogenation to get hydrogenated rosin is 99.86%.

[0073] S2, take the hydrogenated rosin crushing treatment, mixed with glycidyl methacrylate, p-hydroxyanisole and triethylamine in a nitrogen atmosphere, stirring to 88℃, incubation reaction 2 hours, heating to 120℃, incubation reaction 4 hours, to get hydrogenated rosin acrylate derivative; the mass ratio of hydrogenated rosin, glycidyl methacrylate, p-hydroxyanisole, triethylamine is 38:16:0.045:0.065.

[0074] Example 3

[0075] A preparation method of hydrogenated rosin derivative, comprising the following steps:

[0076] S1, take rosin (purchased from Shanghai Titan Science and Technology Co., Ltd.), methyl oleate and deionized water mixed, stirring to dissolve at 90℃, placed in high pressure reactor, adding the catalyst prepared in preparation example 3, sealed, leak detection, with nitrogen and hydrogen each replacement 3 times, heating to 150℃, hydrogen pressure 5MPa, with 500r / min mechanical stirring reaction 2h, cooling, take the product to stand stratification, take the upper oil phase to get hydrogenated rosin; the mass ratio of rosin, methyl oleate, deionized water, catalyst is 1:10:10:0.001; the conversion rate of rosin hydrogenation to get hydrogenated rosin is 99.83%.

[0077] S2, take the hydrogenated rosin broken processing, mixed with glycidyl methacrylate, p-hydroxy anisole and triethylamine in a nitrogen atmosphere, stirring to 88℃, incubation reaction 2 hours, heating to 120℃, incubation reaction 4 hours, get hydrogenated rosin acrylate derivative; the mass ratio of hydrogenated rosin, glycidyl methacrylate, p-hydroxy anisole, triethylamine is 38:16:0.045:0.065.

[0078] Example 4

[0079] A preparation method of hydrogenated rosin derivative, comprising the following steps:

[0080] S1, take rosin (purchased from Shanghai Titan Science and Technology Co., Ltd.), methyl oleate and deionized water mixed, stirring to dissolve at 90℃, placed in high pressure reactor, adding the catalyst prepared in preparation example 4, sealed, leak detection, with nitrogen and hydrogen each replacement 3 times, heating to 150℃, hydrogen pressure 5MPa, with 500r / min mechanical stirring reaction 2h, cooling, take the product to stand stratification, take the upper oil phase to obtain hydrogenated rosin; the mass ratio of rosin, methyl oleate, deionized water, catalyst is 1:10:10:0.001; the conversion rate of rosin hydrogenation to obtain hydrogenated rosin is 83.37%.

[0081] S2, take the hydrogenated rosin broken processing, mixed with glycidyl methacrylate, p-hydroxy anisole and triethylamine in a nitrogen atmosphere, stirring to 88℃, incubation reaction 2 hours, heating to 120℃, incubation reaction 4 hours, get hydrogenated rosin acrylate derivative; the mass ratio of hydrogenated rosin, glycidyl methacrylate, p-hydroxy anisole, triethylamine is 38:16:0.045:0.065.

[0082] Example 5

[0083] A preparation method of hydrogenated rosin derivative, comprising the following steps:

[0084] S1, take rosin (purchased from Shanghai Titan Science and Technology Co., Ltd.), methyl oleate and deionized water mixed, stirring to dissolve at 90℃, placed in high pressure reactor, adding the catalyst prepared in preparation example 5, sealed, leak detection, with nitrogen and hydrogen each replacement 3 times, heating to 150℃, hydrogen pressure 5MPa, with 500r / min mechanical stirring reaction 2h, cooling, take the product to stand stratification, take the upper oil phase to obtain hydrogenated rosin; the mass ratio of rosin, methyl oleate, deionized water, catalyst is 1:10:10:0.001; the conversion rate of rosin hydrogenation to obtain hydrogenated rosin is 67.37%.

[0085] S2, crushing the hydrogenated rosin, mixing with glycidyl methacrylate, p-hydroxyanisole and triethylamine in a nitrogen atmosphere, stirring and heating to 88°C, keeping for 2 hours, heating to 120°C, keeping for 4 hours, to obtain a hydrogenated rosin acrylate derivative; the mass ratio of the hydrogenated rosin, glycidyl methacrylate, p-hydroxyanisole and triethylamine is 38:16:0.045:0.065.

[0086] Application Example 1

[0087] Taking 40g of the hydrogenated rosin acrylate derivative prepared in Example 2, 40g of hydroxypropyl methacrylate, 40g of cyclo-trihydroxymethyl propane formal acrylate, 0.2g of p-hydroxyanisole, 4g of IRGACURE 907, 1g of DEGOSCURE TEGO-450 leveling agent, and 1g of BYK-057 are compounded to prepare a photocuring coating.

[0088] Application Example 2

[0089] Taking 60g of hydroxypropyl methacrylate, 60g of cyclo-trihydroxymethyl propane formal acrylate, 0.2g of p-hydroxyanisole, 4g of IRGACURE 907, 1g of DEGOSCURE TEGO-450 leveling agent, and 1g of BYK-057 are compounded to prepare a photocuring coating.

[0090] Performance Test

[0091] The photocuring coatings prepared in Application Example 1 and Application Example 2 are respectively sprayed on PVC substrates, the film thickness is controlled to be about 20μm, leveled in a 60°C oven for 5min, then cured under ultraviolet light with an irradiation energy of 500mJ / cm 2 , and placed at room temperature for 24h, then the performance test is performed; wherein, the hardness is tested according to the standard GB / T 6739-2006, the adhesion is tested according to the standard GB / T5210-2006, and the wear resistance is tested according to the standard ASTM F2357-04, and the test results are shown in Table 1.

[0092] Table 1

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

[0094] As shown in Table 1, the coating prepared by using the hydrogenated rosin acrylate derivative as a coating monomer has good hardness, adhesion strength and wear resistance.

[0095] The above detailed description of the embodiments of the present application is only for the purpose of illustrating the preferred embodiments of the present application, and should not be considered as limiting the scope of the present application. Any equivalent changes and improvements made to the present application according to the scope of the present application should still fall within the scope of the present application.

Claims

1. A process for the preparation of a hydrogenated rosin derivative, characterized in that, The preparation method of the hydrogenated rosin derivative comprises the following steps: S1, taking the rosin solution to perform hydrogenation reaction under the catalysis of a catalyst to obtain hydrogenated rosin; S2, taking the hydrogenated rosin to perform crushing treatment, mixing with glycidyl methacrylate, p-hydroxyanisole and triethylamine in a nitrogen atmosphere, and performing heat preservation reaction to obtain the hydrogenated rosin derivative; The catalyst comprises a nickel-based active component and a hydrophilic-lipophilic carrier; The hydrophilic-lipophilic carrier comprises a hydrophilic mesoporous silica shell layer and a lipophilic molecular sieve core cavity; The preparation method of the catalyst comprises the following steps: A1, mixing cerium nitrate hexahydrate, deionized water and sodium hydroxide, performing ultrasonic stirring, performing hydrothermal treatment, cooling, centrifugal separation, taking the solid phase to perform washing and drying, adding to a sodium stearate-ethanol aqueous solution, performing water bath heating and stirring, filtering, taking the solid phase to perform washing and drying to obtain material A; A2, uniformly mixing HY type molecular sieve, the material A, sesbania powder, sodium bicarbonate and deionized water, performing extrusion molding, drying, calcining to obtain material B; A3, immersing the material B in an ammonium chloride solution to perform ion exchange, centrifugal separation, taking the solid phase to perform washing and drying to obtain material C; A4, mixing the material C, polydiallyl dimethyl ammonium chloride and deionized water, performing centrifugal separation, taking the solid phase to add to a treatment liquid, performing ultrasonic treatment, adding tetraethyl orthosilicate, stirring, filtering, taking the solid phase to perform washing and drying, grinding, calcining to obtain material D; A5, mixing the material D, nickel acetate and anhydrous ethanol, performing ultrasonic treatment, stirring, centrifugal separation, taking the solid phase to perform washing and vacuum drying, grinding, calcining reduction to obtain the catalyst; 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; the ethanol aqueous solution is prepared by 4mL ethanol and 16mL deionized water; In step A3, the matching ratio of the material B and the ammonium chloride solution is 1g:20-25mL; the concentration of the ammonium chloride solution is 1mol / L; In step A4, the matching ratio of the material C, polydiallyl dimethyl ammonium chloride, deionized water, the treatment liquid and tetraethyl orthosilicate is 3-4g:0.18-0.24g:50mL:300-400mL:3.8-4.8g; the treatment liquid is configured by 500mL ethanol, 3g cetyltrimethylammonium bromide and 10g ammonia water with a mass fraction of 28%; In step A5, the matching ratio of the material D, nickel acetate and anhydrous ethanol is 0.25-0.35g:35-55mg:20-30mL.

2. The method of preparing a hydrogenated rosin derivative according to claim 1, characterized in that, In step S1, the mass ratio of the rosin solution and the catalyst is 21-22:0.001-0.

002.

3. The method for preparing a hydrogenated rosin derivative according to claim 1, characterized in that, In step S2, the mass ratio of the hydrogenated rosin, glycidyl methacrylate, p-hydroxyanisole and triethylamine is 35-40:15-17:0.04-0.05:0.06-0.07.

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