A UV-curable modified epoxy vegetable oil acrylate, its preparation method, and coatings.

Abstract

This invention discloses a method for preparing UV-curable modified epoxy vegetable oil acrylate. The method involves mixing acid anhydride and polyol at a molar ratio of 1:0.8-1.2, followed by rotary evaporation to remove the organic solvent, yielding a hydroxycarboxylic acid. The hydroxycarboxylic acid is then mixed with methacrylic anhydride at a molar ratio of 1:2-5, and the methacrylic acid is removed by rotary evaporation, yielding a carboxyl-containing polyvinyl prepolymer. This carboxyl-containing polyvinyl prepolymer is then reacted with epoxidized vegetable oil in the presence of a catalyst and a polymerization inhibitor until the acid value reaches 2-20 mg KOH / g, followed by cooling and discharge. This invention also discloses the UV-curable modified epoxy vegetable oil acrylate obtained by the above preparation method and a coating. The UV-curable modified epoxy vegetable oil acrylate prepared by this invention has high vinyl functionality, high crosslinking density in the cured coating film, and good alcohol resistance, making it suitable for use in wood, furniture, and plastic coatings.

Description

Technical Field

[0001] This invention relates to the field of UV-curable coating preparation, and particularly to a UV-curable modified epoxy vegetable oil acrylate, its preparation method, and coating. Background Technology

[0002] Since its industrialization in the 1960s, UV (ultraviolet) curing technology has experienced rapid development and has been widely used in coatings, inks, 3D printing, and other fields. Currently, most traditional UV-curable resins are derived from petrochemical resources. With the depletion of global oil resources, utilizing renewable biomass such as vegetable oils to prepare high-performance UV-curable resins is of great significance to the sustainable development of the coatings industry.

[0003] Epoxy vegetable oils are versatile green plasticizers. Acrylates are formed by acrylate oxidation of epoxy vegetable oils to obtain UV-curable epoxy vegetable oil acrylates. One commercially available product is epoxy soybean oil acrylate (AESO), but it suffers from low vinyl (C=C-) functionality, resulting in low crosslinking density of the cured coating and poor chemical resistance.

[0004] Patent application CN 102660170A discloses the application of acrylate-modified epoxidized soybean oil in the preparation of paper printing inks. It involves reacting a hydroxyl-containing acrylate monomer with an acid anhydride to obtain a half-ester intermediate, which is then reacted with epoxidized soybean oil to obtain epoxidized soybean oil-modified acrylate. Patent application CN 102660387A discloses an acrylate-modified epoxidized soybean oil, its preparation method, and its application. This method involves reacting a hydroxyl-containing acrylate monomer with an acid anhydride to obtain a half-ester intermediate, which is then reacted with epoxidized soybean oil. The hydroxyl-containing acrylate monomer is hydroxyethyl acrylate, hydroxyethyl methacrylate, pentaerythritol triacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, trimethylolpropane diacrylate, or trimethylolpropane dimethacrylate. The hydroxyl-containing acrylate monomers used, especially those with high vinyl functionality, are expensive, and the modified products still suffer from defects such as low vinyl functionality, low coating crosslinking density, and insufficient chemical resistance. Summary of the Invention

[0005] To overcome the aforementioned shortcomings and deficiencies of the prior art, the present invention aims to provide a method for preparing UV-curable modified epoxy vegetable oil acrylate. The prepared epoxy vegetable oil acrylate has high vinyl functionality, good film hardness, and chemical resistance. At the same time, the raw materials used are epoxidized vegetable oil, polyols, acid anhydrides, etc., which are widely available, inexpensive, and have low product cost. It does not use high-cost hydroxy acrylic monomers such as pentaerythritol triacrylate and trimethylolpropane diacrylate.

[0006] Another object of the present invention is to provide a UV-curable modified epoxy vegetable oil acrylate prepared by the above preparation method.

[0007] Another object of the present invention is to provide a coating having a high crosslinking density and good chemical resistance in the cured film.

[0008] The objective of this invention is achieved through the following technical solution:

[0009] A method for preparing UV-curable modified epoxy vegetable oil acrylate includes the following steps:

[0010] (1) Preparation of hydroxycarboxylic acid: Acid anhydride and polyol are mixed at a molar ratio of 1:0.8-1.2, organic solvent is added and reacted at 80-100℃ for 2-3 hours. The organic solvent is removed by rotary evaporation to obtain hydroxycarboxylic acid;

[0011] The polyol is a polyol with a hydroxyl functionality of not less than 3;

[0012] (2) Preparation of carboxyl-containing polyvinyl prepolymer: The hydroxycarboxylic acid and methacrylic anhydride are mixed at a molar ratio of 1:2-5, a polymerization inhibitor is added, and the reaction is carried out at 80℃-100℃ for 2-4 hours. The methacrylic acid is removed by rotary evaporation to obtain a carboxyl-containing polyvinyl prepolymer with a vinyl functionality of not less than 2.

[0013] (3) Preparation of UV-curable modified epoxy vegetable oil acrylate: The carboxyl-containing polyvinyl prepolymer and epoxidized vegetable oil are mixed at a molar ratio of carboxyl to epoxy group of 1:1.05-1.50. 0.5-1.5% by mass of catalyst of epoxidized vegetable oil and 0.05-0.5% by mass of polymerization inhibitor of carboxyl-containing polyvinyl prepolymer are added. The mixture is reacted at 80-120℃ until the acid value is 2-20 mg KOH / g. Tripropylene glycol diacrylate is added after cooling. The product is then discharged to obtain UV-curable modified epoxy vegetable oil acrylate.

[0014] Preferably, the acid anhydride is one of phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, adipic anhydride, glutaric anhydride, itaconic anhydride, and maleic anhydride.

[0015] Preferably, the polyol is one of glycerol, trimethylolpropane, pentaerythritol, bistrimethylolpropane, bispentaerythritol, and trifunctional polyether N303.

[0016] Preferably, the epoxidized vegetable oil is one of epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, and epoxidized dehydrated castor oil.

[0017] Preferably, the catalyst is one of N,N-dimethylbenzylamine, triphenylphosphine, tetraethylammonium bromide, and tetrabutylammonium bromide.

[0018] Preferably, the polymerization inhibitor is one of hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, and p-methoxyphenol.

[0019] Preferably, the polymerization inhibitor in step (2) is 0.05-0.5% of methacrylic anhydride.

[0020] The UV-curable modified epoxy vegetable oil acrylate is prepared by the aforementioned method for preparing the UV-curable modified epoxy vegetable oil acrylate.

[0021] A coating comprising the aforementioned UV-curable modified epoxy vegetable oil acrylate.

[0022] Preferably, the coating comprises, by weight parts:

[0023] UV-curable modified vegetable oil acrylate 51.7-79.7 parts; reactive diluent 10-45 parts; photoinitiator 2-5 parts; additives 0.2-0.6 parts.

[0024] Preferably, the reactive diluent is at least one of trimethylolpropane triacrylate, tripropylene glycol diacrylate, hexanediol diacrylate, and 1,4-butanediol diacrylate.

[0025] The photoinitiator is at least one of the following: 2,4,6'-trimethylbenzoyl diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy-cyclohexylphenyl ketone, and isopropylthioxanthraphenone.

[0026] The additives include leveling agents and defoamers.

[0027] Preferably, the amount of tripropylene glycol diacrylate added is 18-22% of the total mass of the UV-curable modified epoxy vegetable oil acrylate.

[0028] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0029] (1) The UV-curable modified epoxy vegetable oil acrylate prepared by this invention has high vinyl functionality. This invention uses a polyol with a hydroxyl functionality of not less than 3 to react with an acid anhydride to generate a hydroxycarboxylic acid. The remaining hydroxyl groups react with methacrylic anhydride to prepare a carboxyl-containing polyvinyl prepolymer with a vinyl functionality of not less than 2. Then, the carboxyl groups react with the epoxy groups of the epoxidized vegetable oil. This results in the consumption of one epoxy group, allowing the introduction of 2 to 5 vinyl groups onto the vegetable oil molecule. In contrast, the traditional reaction of acrylic acid with epoxidized vegetable oil consumes one epoxy group, allowing only one vinyl group to be introduced. Therefore, this invention has a high efficiency in introducing vinyl groups, resulting in a high vinyl functionality of the product molecule. The vinyl functionality of the product can be controlled by adjusting the hydroxyl functionality of the polyol. Furthermore, the type of epoxidized vegetable oil can be optimized, and the vinyl functionality of the product can be controlled by changing the epoxy value. Increasing the vinyl functionality of the product can increase the crosslinking density of its UV-curable coating, thereby improving the chemical resistance of the coating, such as alcohol resistance and water resistance.

[0030] (2) The method for preparing UV-curable modified epoxy vegetable oil acrylate of the present invention can conveniently introduce rigid benzene rings into the product molecules by selecting acid anhydride structures such as acid anhydrides containing benzene rings, which can improve the mechanical properties and hardness of the resin and coating film; the structure and properties of the product resin can be tailored and controlled.

[0031] (3) The method for preparing UV-curable modified epoxy vegetable oil acrylate of the present invention uses epoxidized vegetable oil, polyol, acid anhydride and other raw materials that are widely available, inexpensive and have low product cost. It does not use high-cost pentaerythritol triacrylate and trimethylolpropane diacrylate and other hydroxy acrylic monomers.

[0032] (4) The coating of the present invention can be applied to the fields of wood and plastic coatings. The cured coating film has a high crosslinking density and good alcohol and water resistance. Attached Figure Description

[0033] Figure 1 The infrared spectrum of the modified epoxidized soybean oil acrylate of Example 1 of the present invention is shown. Detailed Implementation

[0034] The present invention will be further described in detail below with reference to the embodiments, but the implementation of the present invention is not limited thereto.

[0035] In each example, the comparative example uses epoxy soybean oil acrylate (AESO) produced by Carpoly Chemicals Group Co., Ltd. to replace the modified epoxy vegetable oil acrylate of the present invention as the resin component of the UV-curable coating. Other components and proportions are the same as in the example.

[0036] In the following examples, the properties of UV-curable modified epoxy vegetable oil acrylate and the formulated coatings were mainly tested using the following methods: The acid value of the UV-curable modified epoxy vegetable oil acrylate resin was determined using the potassium hydroxide titration method according to GB / T 12008.5-2010; the hardness of the coating film was determined according to GB / T 6739-2006; the adhesion of the coating film was determined according to GB / T 9286-1998; the impact resistance of the coating film was determined according to GB / T20624.2-2006; the flexibility of the coating film was determined according to GB / T 1731-1993; the alcohol resistance of the coating film was determined according to GB / T1763-79; the characteristic functional groups on the synthetic monomers were determined by infrared spectroscopy, and the KB pellet method was used, with a pellet thickness of 0.5-1 mm and a scanning range of 4000-500 cm⁻¹. -1 32 scans, 2cm resolution -1 The molecular structure of UV-cured modified epoxy vegetable oil acrylate was characterized.

[0037] Example 1

[0038] Preparation of modified epoxidized soybean oil acrylate in this embodiment:

[0039] Preparation of hydroxycarboxylic acid: 148.12 g (1 mol) of phthalic anhydride and 254.28 g (1 mol) of dipentaerythritol were mixed, and an appropriate amount of organic solvent was added. The mixture was reacted at 80-100 °C for 2-3 h. The organic solvent was removed by rotary evaporation to obtain 402.40 g (1 mol) of hydroxycarboxylic acid.

[0040] Preparation of carboxyl-containing polyvinyl prepolymer: 402.40 g (1 mol) of the above hydroxycarboxylic acid was mixed with 770.80 g (5 mol) of methacrylic anhydride, and 0.2% of p-methoxyphenol of methacrylic anhydride was added. The mixture was reacted at 80℃~100℃ for 2-4 h, and methacrylic acid was removed by rotary evaporation to obtain the carboxyl-containing polyvinyl prepolymer.

[0041] UV-curable modified epoxidized soybean oil acrylate: The above-mentioned carboxyl-containing polyvinyl prepolymer was mixed with epoxidized soybean oil (epoxide value 6.0%) at a carboxyl:epoxy (molar ratio) of 1:1.05. 1.0% (by mass) of triphenylphosphine catalyst (based on the mass fraction of epoxidized vegetable oil) and 0.05% (by mass fraction of p-benzoquinone) of p-vinyl prepolymer were added. The mixture was reacted at 80-120℃ until the acid value was below 20 mg KOH / g. After cooling, 20% (by mass) of tripropylene glycol diacrylate (TPGDA) was added, and the product was discharged to obtain UV-curable modified epoxidized soybean oil acrylate. Its properties are: light yellow transparent liquid, viscosity (25℃): 9230 mPa.s; acid value: 15.6 mg KOH / g.

[0042] 2. Preparation of UV-curable epoxy soybean oil acrylate coating

[0043] The ingredients for this embodiment are shown in Table 1 below:

[0044]

[0045] According to the formula in Table 1, UV-curable modified epoxy dehydrated soybean oil acrylate, reactive diluent, leveling agent, and defoamer are added sequentially to a material dispersion tank. The mixture is stirred for 5-10 minutes using a GFJ-0.4 high-speed disperser at a speed of 1000-500 r / min to obtain a UV-curable modified epoxy vegetable oil acrylate coating. After standing until the bubbles escape, a 25 μm wet film coater is used to prepare a coating film on a glass plate, wooden board, and tinplate, at a speed of 600 mJ / cm². 2 The coating was irradiated with a UV lamp for 15 seconds to test its performance. The coating performance is shown in Table 2 below. At the same time, the same commercially available epoxy soybean oil acrylate (AESO) was used to prepare the coating according to the formula in Table 1. The coating was formed under the same curing conditions, and the coating performance was tested. The coating performance is shown in Table 2.

[0046] Table 2

[0047]

[0048]

[0049] Figure 1 The infrared spectra of the product molecules show a value of 2937 cm⁻¹. -1 The absorption peak of the methyl CH stretching vibration near the 2860 cm⁻¹ -1 The nearby methylene CH stretching vibration absorption peak and 1735 cm⁻¹ -1 The absorption peak of the ester carbonyl group is located near 3481 cm⁻¹. -1 and 3499cm -1 The hydroxyl absorption peak at 908 cm⁻¹ is significantly enhanced; in the spectrum, the absorption peak at 908 cm⁻¹ is significantly enhanced. -1 The characteristic absorption peak attributed to the epoxy group disappeared, indicating that the epoxy group in the vegetable oil underwent a ring-opening reaction with the carboxyl group, leading to the disappearance of the epoxy group's absorption peak and the enhancement of the hydroxyl absorption peak. Furthermore, the carbon-carbon double bond stretching vibration peak in the product spectrum is located at 1635 cm⁻¹. -1 The presence of these characteristic absorption peaks indicates that the carbon-carbon double bonds have been successfully grafted. These characteristic absorption peaks confirm the successful preparation of modified epoxidized soybean oil acrylate.

[0050]

[0051] Formula 1 describes the reaction of equimolar amounts of phthalic anhydride with dipentaerythritol, yielding a product containing carboxyl and 5 hydroxyl groups. This product then reacts with 5 moles of methacrylic anhydride, resulting in a product containing 1 carboxyl group and 5 vinyl functional groups. Further reaction with epoxidized soybean oil results in the carboxyl group reacting with the epoxy group, consuming one epoxy group and introducing 5 vinyl groups. Traditional reactions of acrylic acid with epoxidized soybean oil consume one epoxy group and introduce only 1 vinyl group. Clearly, this patent significantly improves the efficiency of introducing vinyl groups into the soybean oil molecule, while also producing a product with high vinyl functionality. Table 2, comparing the coating properties, shows that the cured coating of this embodiment exhibits superior hardness and alcohol resistance compared to traditional AESO coatings.

[0052] Compared to patent CN 102660170A, this invention consumes one epoxy group while introducing five vinyl groups, resulting in high vinyl group introduction efficiency and high vinyl functionality of the obtained product. Patent CN 102660170A uses a hydroxyl-containing acrylate monomer reacted with an anhydride to obtain a half-ester intermediate, which is then reacted with epoxidized soybean oil. This process consumes one epoxy group and can only introduce one vinyl group, resulting in low vinyl group introduction efficiency and low vinyl functionality of the obtained product. Patent CN 102660387A discloses a process where a hydroxyl-containing acrylate monomer reacts with an anhydride to obtain a half-ester intermediate, which is then reacted with epoxidized soybean oil. This process consumes one epoxy group and can introduce a maximum of three vinyl groups (when using pentaerythritol triacrylate), which is lower than the one epoxy group consumed in this embodiment, allowing for the introduction of five vinyl groups. Furthermore, the raw materials used in patent CN 102660387A, such as pentaerythritol triacrylate and trimethylolpropane diacrylate, are expensive, leading to high production costs. This embodiment uses conventional raw materials, resulting in low cost and good practicality.

[0053] Example 2

[0054] Preparation of modified epoxy linseed oil acrylate in this embodiment:

[0055] Preparation of hydroxycarboxylic acid: 100.07 g (1 mol) of succinic anhydride and 92.09 g (1 mol) of glycerol were added with an appropriate amount of organic solvent and reacted at 80-100 °C for 2-3 h. The organic solvent was removed by rotary evaporation to obtain 192.16 g (1 mol) of hydroxycarboxylic acid.

[0056] Preparation of carboxyl-containing polyvinyl prepolymer: 192.16 g (1 mol) of the above hydroxycarboxylic acid and 308.32 g (2 mol) of methacrylic anhydride were added, and 0.1% hydroquinone of methacrylic anhydride was added. The mixture was reacted at 80℃~100℃ for 2-4 h. The methacrylic acid was removed by rotary evaporation to obtain the carboxyl-containing polyvinyl prepolymer.

[0057] UV-curable modified epoxy linseed oil acrylate: A carboxyl-containing polyvinyl prepolymer is mixed with epoxidized linseed oil (epoxy value 7.1%) at a carboxyl:epoxy molar ratio of 1:1.1. 1.5% (by weight) of N,N-dimethylbenzylamine catalyst (by weight of epoxidized vegetable oil) and 0.1% (by weight of polyvinyl prepolymer) of hydroquinone are added. The mixture is reacted at 80-120℃ until the acid value is below 20 mg KOH / g. After cooling, 20% (by weight of total resin) of tripropylene glycol diacrylate (TPGDA) is added, and the product is discharged to obtain UV-curable modified epoxy linseed oil acrylate. Its properties are: yellow transparent liquid, viscosity (25℃): 6210 mPa.s; acid value: 16.0 mg KOH / g.

[0058] 2. Preparation of UV-curable epoxy linseed oil acrylate coating

[0059] The ingredients for this embodiment are shown in Table 3 below:

[0060]

[0061] According to the formula in Table 3, the UV-curable modified epoxy linseed oil acrylate, reactive diluent, leveling agent, and defoamer are added sequentially to the material dispersion tank. The mixture is stirred for 5-10 minutes using a GFJ-0.4 high-speed disperser at a speed of 1000-500 r / min to obtain a UV-curable modified epoxy linseed oil acrylate coating. After standing until the bubbles escape, a 25 μm wet film coater is used to prepare a coating film on a glass plate, wooden board, and tinplate, at a speed of 600 mJ / cm². 2 The coating was irradiated with a UV lamp for 15 seconds to test its performance. The coating performance is shown in Table 4 below. At the same time, the same commercially available epoxy soybean oil acrylate (AESO) was used to prepare the coating according to the formula in Table 3. The coating was formed under the same curing conditions, and the coating performance was tested. The coating performance is shown in Table 4.

[0062] Table 4

[0063]

[0064] Example 3

[0065] Preparation of modified epoxy tung oil acrylate in this embodiment:

[0066] Preparation of hydroxycarboxylic acid: 128.13 g (1 mol) of adipic anhydride was mixed with 134.17 g (1 mol) of trimethylolpropane, and an appropriate amount of organic solvent was added. The mixture was reacted at 80-100 °C for 2-3 h. The organic solvent was removed by rotary evaporation to obtain 262.30 g (1 mol) of hydroxycarboxylic acid.

[0067] Preparation of carboxyl-containing polyvinyl prepolymer: 262.30 g (1 mol) of the above-mentioned hydroxycarboxylic acid and 308.32 g (2 mol) of methacrylic anhydride were added to 0.2% p-hydroxyanisole of methacrylic anhydride and reacted at 80℃~100℃ for 2-4 h. The methacrylic acid was removed by rotary evaporation to obtain the carboxyl-containing polyvinyl prepolymer.

[0068] UV-curable modified epoxy tung oil acrylate: A polyvinyl prepolymer containing carboxyl groups is mixed with epoxidized tung oil (epoxy value 8.5%) at a carboxyl:epoxy molar ratio of 1:1.50. 0.8% (by weight) of tetraethylammonium bromide catalyst (based on the mass fraction of epoxidized vegetable oil) and 0.2% (by weight) of p-hydroxyanisole (by mass fraction of the polyvinyl prepolymer) are added. The mixture is reacted at 80-120℃ until the acid value is below 20 mg KOH / g. After cooling, 20% (by weight) of tripropylene glycol diacrylate (TPGDA) is added, and the product is discharged to obtain UV-curable modified epoxy tung oil acrylate. Its properties are: yellowish-brown transparent liquid, viscosity (25℃): 7570 mPa.s; acid value: 15.6 mg KOH / g.

[0069] 2. Preparation of UV-curable epoxy tung oil acrylate coatings

[0070] The ingredients for this embodiment are shown in Table 5 below:

[0071]

[0072] According to the formula in Table 5, the UV-curable modified epoxy tung oil acrylate, reactive diluent, leveling agent, and defoamer are added sequentially to the material dispersion tank. The mixture is stirred for 5-10 minutes using a GFJ-0.4 high-speed disperser at a speed of 1000-500 r / min to obtain the UV-curable modified epoxy tung oil acrylate coating. After standing until the bubbles escape, a 25 μm wet film coater is used to prepare the coating on glass plates, wooden boards, and tinplate, at a speed of 600 mJ / cm². 2 The coating was irradiated with a UV lamp for 15 seconds to test its performance. The coating performance is shown in the table below. At the same time, the same commercially available epoxy soybean oil acrylate (AESO) was used to prepare the coating according to the formula in Table 5. The coating was formed under the same curing conditions, and the coating performance was tested. The results are shown in Table 6.

[0073] Table 6

[0074]

[0075] Example 4

[0076] Preparation of modified epoxy dehydrated castor oil acrylate in this embodiment:

[0077] Preparation of hydroxycarboxylic acid: 114.10 g (1 mol) of glutaric anhydride was mixed with 250.33 g (1 mol) of bis(trimethylolpropane), and an appropriate amount of organic solvent was added. The mixture was reacted at 80-100 °C for 2-3 h. The organic solvent was removed by rotary evaporation to obtain 364.43 g (1 mol) of hydroxycarboxylic acid.

[0078] Preparation of carboxyl-containing polyvinyl prepolymer: 364.43 g (1 mol) of the above-mentioned hydroxycarboxylic acid was mixed with 462.48 g (3 mol) of methacrylic anhydride, and 0.5% of p-methoxyanisole of methacrylic anhydride was added. The mixture was reacted at 80℃~100℃ for 4 h, and methacrylic acid was removed by rotary evaporation to obtain the carboxyl-containing polyvinyl prepolymer.

[0079] UV-curable modified epoxy-cured dehydrated castor oil acrylate: A carboxyl-containing polyvinyl prepolymer is mixed with epoxidized dehydrated castor oil (epoxy value 5.5%) at a carboxyl:epoxy molar ratio of 1:1.25. 0.5% (by weight of the epoxidized dehydrated castor oil) of tetrabutylammonium bromide catalyst and 0.5% (by weight of the polyvinyl prepolymer) of methylhydroquinone are added. The mixture is reacted at 80-120℃ until the acid value is below 20 mg KOH / g. After cooling, 20% (by weight of the total resin) of tripropylene glycol diacrylate (TPGDA) is added. The product is then discharged to obtain UV-curable modified epoxy-cured dehydrated castor oil acrylate. Its properties are: light yellow transparent liquid, viscosity (25℃): 52860 mPa.s; acid value: 18 mg KOH / g.

[0080] 2. Preparation of UV-curable epoxy dehydrated castor oil acrylate coating

[0081] The ingredients for this embodiment are shown in Table 7 below:

[0082]

[0083] According to the formula in Table 7, UV-curable modified epoxy dehydrated castor oil acrylate, reactive diluent, leveling agent, and defoamer are added sequentially to a material dispersion tank. The mixture is stirred for 5-10 minutes using a GFJ-0.4 high-speed disperser at a speed of 1000-500 r / min to obtain a UV-curable modified epoxy vegetable oil acrylate coating. After standing until the bubbles escape, a 25 μm wet film coater is used to prepare a coating film on a glass plate, wooden board, and tinplate, at a speed of 600 mJ / cm². 2 The coating was irradiated with a UV lamp for 15 seconds to test its performance. The coating performance is shown in Table 8 below. At the same time, the same commercially available epoxy soybean oil acrylate (AESO) was used to prepare the coating according to the formula in Table 7. The coating was formed under the same curing conditions, and the coating performance was tested. The results are shown in Table 8.

[0084] Table 8

[0085]

[0086]

[0087] Example 5

[0088] Preparation of modified epoxidized soybean oil acrylate in this embodiment

[0089] Preparation of hydroxycarboxylic acid: 112.19 g (1 mol) of itaconic anhydride and 136.15 g (1 mol) of pentaerythritol were mixed, and an appropriate amount of organic solvent was added. The mixture was reacted at 80-100 °C for 2-3 h. The organic solvent was removed by rotary evaporation to obtain 248.34 g (1 mol) of hydroxycarboxylic acid.

[0090] Preparation of carboxyl-containing polyvinyl prepolymer: 248.34 g (1 mol) of the above hydroxycarboxylic acid was mixed with 462.48 g (3 mol) of methacrylic anhydride, and 0.3% of p-methoxyphenol of methacrylic anhydride was added. The mixture was reacted at 80℃~100℃ for 4 h, and methacrylic acid was removed by rotary evaporation to obtain the carboxyl-containing polyvinyl prepolymer.

[0091] UV-curable modified epoxidized soybean oil acrylate: A carboxyl-containing polyvinyl prepolymer is mixed with epoxidized soybean oil (epoxide value 6.0%) at a carboxyl:epoxy group (molar ratio) of 1:1.15. 1.2% (by weight of the epoxidized vegetable oil) of triphenylphosphine catalyst and 0.3% (by weight of the polyvinyl prepolymer) of p-methoxyphenol are added. The mixture is reacted at 80-120℃ until the acid value is below 20 mg KOH / g. After cooling, 20% (by weight of the total resin) of tripropylene glycol diacrylate (TPGDA) is added, and the product is discharged to obtain UV-curable modified epoxidized soybean oil acrylate. Its properties are: brownish-red transparent liquid, viscosity (25℃): 42210 mPa.s; acid value: 15.6 mg KOH / g.

[0092] 2. Preparation of UV-curable epoxy soybean oil acrylate coating

[0093] The ingredient list for this embodiment is shown in Table 9 below:

[0094]

[0095]

[0096] According to the formula in Table 9, UV-curable modified epoxy soybean oil acrylate, reactive diluent, leveling agent, and defoamer are added sequentially to a material dispersion tank. The mixture is stirred for 5-10 minutes using a GFJ-0.4 high-speed disperser at a speed of 1000-500 r / min to obtain a UV-curable modified epoxy vegetable oil acrylate coating. After standing until the bubbles escape, a 25 μm wet film coater is used to prepare a coating film on a glass plate, wooden board, and tinplate, at a speed of 600 mJ / cm².2 The coating was irradiated with a UV lamp for 15 seconds to test its performance. The coating performance is shown in Table 10 below. At the same time, the same commercially available epoxy soybean oil acrylate (AESO) was used to prepare the coating according to the formula in Table 9. The coating was formed under the same curing conditions, and the coating performance was tested. The results are shown in Table 10.

[0097] Table 10

[0098]

[0099] Example 6

[0100] Preparation of modified epoxidized soybean oil acrylate in this embodiment:

[0101] Preparation of hydroxycarboxylic acid: 154.16 g (1 mol) of methylhexahydrophthalic anhydride was mixed with 300 g (1 mol) of polyether N303, and an appropriate amount of organic solvent was added. The mixture was reacted at 80-100℃ for 2-3 h. The organic solvent was removed by rotary evaporation to obtain 454.16 g (1 mol) of hydroxycarboxylic acid.

[0102] Preparation of carboxyl-containing polyvinyl prepolymer: 454.16 (1 mol) of the above hydroxycarboxylic acid was mixed with 308.32 g (2 mol) of methacrylic anhydride, and 0.3% p-benzoquinone of methacrylic anhydride was added. The mixture was reacted at 80℃~100℃ for 2-4 h, and methacrylic acid was removed by rotary evaporation to obtain the carboxyl-containing polyvinyl prepolymer.

[0103] UV-curable modified epoxidized soybean oil acrylate: The above-mentioned carboxyl-containing polyvinyl prepolymer was mixed with epoxidized soybean oil (epoxide value 6.0%) at a carboxyl:epoxide molar ratio of 1:1.1. 0.8% (by mass) of the epoxidized vegetable oil catalyst N,N-dimethylbenzylamine and 0.3% (by mass) of the polyvinyl prepolymer p-benzoquinone were added. The mixture was reacted at 80-120℃ until the acid value was below 20 mg KOH / g. After cooling, 20% (by mass) of tripropylene glycol diacrylate (TPGDA) was added, and the product was discharged to obtain UV-curable modified epoxidized soybean oil acrylate. Its properties are: light yellow transparent liquid, viscosity (25℃): 2150 mPa.s; acid value: 18.6 mg KOH / g.

[0104] 2. Preparation of UV-curable epoxy soybean oil acrylate coating

[0105] The ingredients for this embodiment are shown in Table 11 below:

[0106]

[0107] According to the formula in Table 11, UV-curable modified epoxy soybean oil acrylate, reactive diluent, leveling agent, and defoamer are added sequentially to a material dispersion tank. The mixture is stirred for 5-10 minutes using a GFJ-0.4 high-speed disperser at a speed of 1000-500 r / min to obtain a UV-curable modified epoxy vegetable oil acrylate coating. After standing until bubbles escape, a 25 μm wet film coater is used to prepare a coating film on a glass plate, wooden board, and tinplate, at a speed of 600 mJ / cm². 2 The coating was irradiated with a UV lamp for 15 seconds to test its performance. The coating performance is shown in Table 12 below. At the same time, the same commercially available epoxy soybean oil acrylate (AESO) was used to prepare the coating according to the formula in Table 11. The coating was formed under the same curing conditions, and the coating performance was tested. The results are shown in Table 12.

[0108] Table 12

[0109]

[0110]

[0111] Example 7

[0112] Preparation of modified epoxy linseed oil acrylate in this embodiment:

[0113] Preparation of hydroxycarboxylic acid: 168.19 g (1 mol) of methylhexahydrophthalic anhydride was mixed with 254.28 g (1 mol) of dipentaerythritol, and an appropriate amount of organic solvent was added. The mixture was reacted at 80-100 °C for 2-3 h. The organic solvent was removed by rotary evaporation to obtain 423.47 g (1 mol) of hydroxycarboxylic acid.

[0114] Preparation of carboxyl-containing polyvinyl prepolymer: 423.47 g (1 mol) of the above hydroxycarboxylic acid was mixed with 770.80 g (5 mol) of methacrylic anhydride, and 0.08% hydroquinone of methacrylic anhydride was added. The mixture was reacted at 80℃~100℃ for 2-4 h, and methacrylic acid was removed by rotary evaporation to obtain the carboxyl-containing polyvinyl prepolymer.

[0115] UV-curable modified epoxy linseed oil acrylate: The above-mentioned carboxyl-containing polyvinyl prepolymer was mixed with epoxy linseed oil (epoxy value 7.1%) at a carboxyl:epoxy molar ratio of 1:1.1. 1.0% (by weight of the epoxidized vegetable oil) of triphenylphosphine catalyst and 0.08% (by weight of the polyvinyl prepolymer) of hydroquinone were added. The mixture was reacted at 80-120℃ until the acid value was below 20 mg KOH / g. After cooling, 20% (by weight of the total resin) of tripropylene glycol diacrylate (TPGDA) was added, and the product was discharged to obtain UV-curable modified epoxy linseed oil acrylate. Its properties are: light yellow transparent liquid, viscosity (25℃): 7844 mPa.s; acid value 17.6 mg KOH / g.

[0116] 2. Preparation of UV-curable epoxy linseed oil acrylate coating

[0117] The ingredients for this embodiment are shown in Table 13 below:

[0118]

[0119]

[0120] According to the formula in Table 13, UV-curable modified epoxy linseed oil acrylate, reactive diluent, leveling agent, and defoamer are added sequentially to a material dispersion tank. The mixture is stirred for 5-10 minutes using a GFJ-0.4 high-speed disperser at a speed of 1000-500 r / min to obtain a UV-curable modified epoxy vegetable oil acrylate coating. After standing until bubbles escape, a 25 μm wet film coater is used to prepare a coating film on a glass plate, wooden board, and tinplate, at a speed of 600 mJ / cm². 2 The coating was irradiated with a UV lamp for 15 seconds to test its performance. The coating performance is shown in Table 14 below. At the same time, the same commercially available epoxy soybean oil acrylate (AESO) was used to prepare the coating according to the formula in Table 13. The coating was formed under the same curing conditions, and the coating performance was tested. The coating performance is shown in Table 14.

[0121] Table 14

[0122]

[0123] Example 8

[0124] Preparation of modified epoxidized soybean oil acrylate in this embodiment

[0125] Preparation of hydroxycarboxylic acid: 98.06 g (1 mol) of maleic anhydride was mixed with 134.17 g (1 mol) of trimethylolpropane, and an appropriate amount of organic solvent was added. The mixture was reacted at 80-100 °C for 2-3 h. The organic solvent was removed by rotary evaporation to obtain 232.23 g (1 mol) of hydroxycarboxylic acid.

[0126] Preparation of carboxyl-containing polyvinyl prepolymer: 232.23 g (1 mol) of the above-mentioned hydroxycarboxylic acid was mixed with 308.32 g (2 mol) of methacrylic anhydride, and 0.2% p-methoxyphenol of methacrylic anhydride was added. The mixture was reacted at 80℃~100℃ for 2-4 h, and methacrylic acid was removed by rotary evaporation to obtain the carboxyl-containing polyvinyl prepolymer.

[0127] UV-curable modified epoxidized soybean oil acrylate: The above-mentioned carboxyl-containing polyvinyl prepolymer was mixed with epoxidized soybean oil (epoxide value 6.0%) at a carboxyl:epoxy molar ratio of 1:1.05. 1.5% (by mass) of triphenylphosphine catalyst (based on the mass fraction of epoxidized vegetable oil) and 0.3% (by mass fraction of p-benzoquinone) of p-vinyl prepolymer were added. The mixture was reacted at 80-120℃ until the acid value was below 20 mg KOH / g. After cooling, 20% (by mass) of tripropylene glycol diacrylate (TPGDA) was added, and the product was discharged to obtain UV-curable modified epoxidized soybean oil acrylate. Its properties are: dark red transparent liquid, viscosity (25℃): 48210 mPa.s; acid value: 15.8 mg KOH / g.

[0128] 2. Preparation of UV-curable epoxy soybean oil acrylate coating

[0129] The ingredients for this embodiment are shown in Table 15 below:

[0130]

[0131] According to the formula in Table 15, UV-curable modified epoxy soybean oil acrylate, reactive diluent, leveling agent, and defoamer are added sequentially to a material dispersion tank. The mixture is stirred for 5-10 minutes using a GFJ-0.4 high-speed disperser at a speed of 1000-500 r / min to obtain a UV-curable modified epoxy vegetable oil acrylate coating. After standing until the bubbles escape, a 25 μm wet film coater is used to prepare a coating film on a glass plate, wooden board, and tinplate, at a speed of 600 mJ / cm². 2 The coating was irradiated with a UV lamp for 15 seconds to test its performance. The coating performance is shown in Table 16 below. At the same time, the same commercially available epoxy soybean oil acrylate (AESO) was used to prepare the coating according to the formula in Table 15. The coating was formed under the same curing conditions, and the coating performance was tested. The coating performance is shown in Table 16.

[0132] Table 16

[0133]

[0134] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the embodiments described above. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for preparing UV-curable modified epoxy vegetable oil acrylate, characterized in that, Includes the following steps: (1) Preparation of hydroxycarboxylic acid: Acid anhydride and polyol are mixed at a molar ratio of 1:0.8-1.2, organic solvent is added and reacted at 80-100℃ for 2-3 h, and the organic solvent is removed by rotary evaporation to obtain hydroxycarboxylic acid; The polyol is one of glycerol, trimethylolpropane, pentaerythritol, bis(trimethylolpropane), bis(pentaerythritol), and trifunctional polyether N303; the anhydride is one of phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, adipic anhydride, glutaric anhydride, itaconic anhydride, and maleic anhydride. (2) Preparation of carboxyl-containing polyvinyl prepolymer: The hydroxycarboxylic acid and methacrylic anhydride are mixed at a molar ratio of 1:2-5, a polymerization inhibitor is added, and the mixture is reacted at 80℃-100℃ for 2-4 hours. The methacrylic acid is removed by rotary evaporation to obtain a carboxyl-containing polyvinyl prepolymer with a vinyl functionality of not less than 2. (3) Preparation of UV-curable modified epoxy vegetable oil acrylate: The carboxyl-containing polyvinyl prepolymer and epoxidized vegetable oil are mixed at a molar ratio of carboxyl to epoxy group of 1:1.05-1.

50. 0.5-1.5% by mass of catalyst of epoxidized vegetable oil and 0.05-0.5% by mass of polymerization inhibitor of carboxyl-containing polyvinyl prepolymer are added. The mixture is reacted at 80-120℃ until the acid value is 2-20 mg KOH / g. The mixture is then cooled and tripropylene glycol diacrylate is added. The product is discharged to obtain UV-curable modified epoxy vegetable oil acrylate. The epoxidized vegetable oil is one of epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, and epoxidized dehydrated castor oil.

2. The method for preparing UV-curable modified epoxy vegetable oil acrylate according to claim 1, characterized in that, The catalyst is one of N,N-dimethylbenzylamine, triphenylphosphine, tetraethylammonium bromide, and tetrabutylammonium bromide.

3. The method for preparing UV-curable modified epoxy vegetable oil acrylate according to claim 1, characterized in that, The polymerization inhibitor is one of hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, and p-methoxyphenol.

4. A UV-curable modified epoxy vegetable oil acrylate, characterized in that, It is prepared by the method for preparing UV-curable modified epoxy vegetable oil acrylate according to any one of claims 1-3.

5. A coating, characterized in that, It includes the UV-curable modified epoxy vegetable oil acrylate as described in claim 4.

6. The coating according to claim 5, characterized in that, By weight, including: UV-curable modified vegetable oil acrylate 51.7-79.7 parts; reactive diluent 10-45 parts; photoinitiator 2-5 parts; additives 0.2-0.6 parts.

7. The coating according to claim 6, characterized in that, The active diluent is at least one of trimethylolpropane triacrylate, tripropylene glycol diacrylate, hexanediol diacrylate, and 1,4-butanediol diacrylate. The photoinitiator is at least one of the following: 2,4,6'-trimethylbenzoyl diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy-cyclohexylphenyl ketone, and isopropylthioxanthraphenone. The additives include leveling agents and defoamers.

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