Composite anhydride modified UV-curable epoxy acrylate, and preparation method therefor and use thereof

Abstract

A composite anhydride modified UV-curable epoxy acrylate, and a preparation method therefor and the use thereof. The preparation method comprises the following steps: heating glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin, part of a catalyst, and part of a polymerization inhibitor to 75°C-80°C with stirring and maintaining the temperature for 0.8-1.2 h; then, increasing the temperature in stages, adding the remaining catalyst and polymerization inhibitor in batches, and finally increasing the temperature to 115°C-125°C and reacting for 4-5 h to obtain the composite anhydride modified UV-curable epoxy acrylate. The preparation method is low in terms of price and low in terms of product cost, does not use any solvent in the reaction process, and reduces VOC emissions. The prepared epoxy acrylate has high functionality, and good hardness, adhesion, flexibility, impact resistance and chemical resistance after film formation.

Description

A composite anhydride modified UV-curable epoxy acrylate and its preparation method and application TECHNICAL FIELD

[0001] The present application relates to the field of preparation of UV-curable epoxy acrylate coatings, in particular to a composite anhydride modified UV-curable epoxy acrylate and its preparation method and application. BACKGROUND

[0002] UV (ultraviolet) curing technology refers to a process in which under the irradiation of ultraviolet light, the photoinitiator in the system absorbs energy to produce free radicals or cations, which in turn initiate the grafting, polymerization, crosslinking and other chemical reactions of oligomers and active diluents containing active groups, thereby promoting the rapid solidification of the substrate surface into a film. Unlike existing traditional coatings such as solvent-based, water-based and heat-cured coatings, UV curing technology has the advantage of fast curing speed of the paint film, does not require the use of solvents, is simple to operate, and the curing process is not easily affected by temperature, environment and other factors. With the gradual change of China's industry towards green environmental protection, high efficiency and energy saving, and intelligentization, the industrial application of UV curing technology has developed rapidly.

[0003] Epoxy acrylate resin is the most commonly used UV light curing resin, and bisphenol A epoxy acrylate is the fastest curing speed among the epoxy acrylate oligomers and is the most commonly used one. Due to the presence of rigid benzene ring structure in the structure, the UV cured coating film has high brittleness, poor flexibility, and poor weather resistance, light aging resistance and yellowing resistance. In order to solve these defects, Chinese invention patent CN102295730A discloses a synthesis method of intramolecular toughening epoxy vinyl ester resin. First, long-chain saturated dibasic acid is reacted with flexible dibasic alcohol to obtain carboxyl-terminated long-chain saturated dibasic acid monoester, and then reacted with epoxy resin and unsaturated monocarboxylic acid until the acid value is reduced to below 10 mgKOH / g. The advantage of this method is that flexible molecular chains are introduced into the main chain of the resin, thereby improving the toughness of the resin. The disadvantage is that the introduction of dibasic acid monoester increases the molecular weight and viscosity of the resin, and the amount used is large. The increased viscosity of the resin makes it unstable in storage, and the hardness of the coating film is reduced, and the toughening effect is poor. Patent application CN104558522A discloses a modification method of modified epoxy acrylate. Bisphenol A type epoxy resin and 1,2-cyclohexanediol diglycidyl ether are reacted to form a modified epoxy resin. The synthesis method is to add the above two materials and a catalyst to a reaction container, stir and heat to 80-90℃, gradually add the mixture of acrylic acid and polymerization inhibitor within 0.5-1h, then gradually heat until the acid value is reduced to below 3.0 mgKOH / g, to obtain the modified epoxy acrylate. Although this patent solves the problems of high resin viscosity, high brittleness and poor flexibility of the coating film, the patent actually achieves this goal by physically blending 1,2-cyclohexanediol diglycidyl ether dipropylene acrylate into ordinary epoxy acrylate resin, which easily reduces the hardness of the coating film. Therefore, it is an urgent technical problem in the field to develop a modified epoxy acrylate resin with high hardness, high toughness and good flexibility.

[0004] SUMMARY

[0005] In order to overcome the above-mentioned shortcomings and deficiencies of the prior art, the purpose of the present application is to provide a preparation method of a composite anhydride modified UV light curable epoxy acrylate, which is low in price and low in product cost, does not use any solvent in the reaction process, reduces VOC emission, and has high hardness, excellent adhesion, flexibility, impact resistance and chemical resistance after being cured into a film.

[0006] Another purpose of the present application is to provide a composite anhydride modified UV light curable epoxy acrylate.

[0007] Still another purpose of the present application is to provide the application of the above-mentioned composite anhydride modified UV light curable epoxy acrylate for preparing a coating, and the cured coating film has high hardness, excellent flexibility and impact resistance, chemical resistance, heat resistance and fast curing speed.

[0008] The object of the present application is achieved by the following technical solutions.

[0009] The present application provides a preparation method of a composite anhydride modified UV light curable epoxy acrylate, comprising the following steps:

[0010] (1) according to the following formula, the raw materials are weighed by weight parts:

[0011] (2) the glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin, part of the catalyst, part of the polymerization inhibitor are stirred and heated to 75-80℃ and kept for 0.8-1.2h, then the remaining catalyst and the remaining polymerization inhibitor are added in batches by subsection heating, and finally heated to 115-125℃ for 4-5h to obtain a composite anhydride modified UV light curable epoxy acrylate;

[0012] The weight of the part of the catalyst is 55%-65% of the total weight of the catalyst; the weight of the part of the polymerization inhibitor is 55%-65% of the total weight of the polymerization inhibitor.

[0013] Preferably, the epoxy resin is one of epoxy resin E51, E44, F44, F51, 170, 128, R-828, S-21, BD-20.

[0014] Preferably, the catalyst is at least one of tetraethylammonium bromide, tetrabutylammonium bromide, N,N dimethyl benzylamine and triphenylphosphine.

[0015] Preferably, the polymerization inhibitor is at least one of p-hydroxyanisole, p-benzoquinone, methylhydroquinone, hydroquinone, 2,5-dimethylhydroquinone.

[0016] Preferably, the subsection heating and the remaining catalyst and the remaining polymerization inhibitor are added in batches, specifically:

[0017] Every 0.8-1.2h, the temperature is raised by 8-10℃; the remaining catalyst and the remaining polymerization inhibitor are added in 4-5 times.

[0018] The present application also provides a composite anhydride modified UV light curable epoxy acrylate, comprising, by weight parts:

[0019] The present application also provides the application of the composite anhydride modified UV light curable epoxy acrylate, which is used for preparing a coating.

[0020] Preferably, the coating comprises 65-87 parts of the composite anhydride modified UV curable epoxy acrylate, 10-30 parts of the active diluent and 3-5 parts of the photoinitiator.

[0021] Preferably, the active diluent is one of tripropylene glycol diacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, hexanediol diacrylate, triethylene glycol diacrylate.

[0022] Preferably, the photoinitiator is at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, 1-hydroxycyclohexyl phenyl ketone.

[0023] Compared with the prior art, the present application has the following advantages and beneficial effects:

[0024] (1) The present application introduces a vinyl group into a monocarboxylic acid intermediate by reacting a vinyl-containing carboxyl intermediate generated from pimelic anhydride, maleic anhydride and phthalic anhydride with hydroxyethyl acrylate, introduces a rigid benzene ring, improves the vinyl functionality and the content of rigid benzene ring of the modified epoxy acrylate product, and improves the crosslinking density, hardness and chemical resistance of the UV-cured coating film.

[0025] (2) The present application combines rigid structures and flexible long chains by compounding pimelic anhydride, maleic anhydride and phthalic anhydride and reasonably limiting the ratio thereof, and optimizes and improves the problems of high hardness, high flexibility and high impact resistance of the UV-cured coating film.

[0026] (3) The UV-curable epoxy acrylate prepared by the one-step method of the present application has simple synthesis process, mild reaction conditions, low operation difficulty in industry, wide source and low price of raw materials, and low preparation cost of the resin, and the coating prepared from the resin can be directly applied to UV curing, and has the prospect of large-scale production in industry.

[0027] (4) The composite anhydride modified UV-curable epoxy acrylate of the present application can be applied to many fields such as primer topcoat, plastic paint and printing ink, has high crosslinking density, high hardness and good flexibility, and has excellent chemical resistance of the coating film. BRIEF DESCRIPTION OF DRAWINGS

[0028] Fig. 1 is an infrared spectrum of the composite anhydride modified UV-curable epoxy acrylate in Example 1 of the present application.

[0029] Fig. 2 is a nuclear magnetic hydrogen spectrum of the composite anhydride modified UV-curable epoxy acrylate in Example 1 of the present application.

[0030] Fig. 3 is a gel chromatogram of the composite anhydride modified UV-curable epoxy acrylate in Example 1 of the present application.

[0031] Fig. 4 is a synthesis flowchart of the composite anhydride modified UV-curable epoxy acrylate in Example 1 of the present application. Detailed Implementation

[0032] 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.

[0033] The comparative examples in each embodiment use EA resin produced by Beixin Carpoly Chemical Group Co., Ltd. to replace the modified epoxy acrylate of the present invention as the oligomer component of the UV-curable coating, and the other components and proportions are the same as in the respective embodiments.

[0034] In the following examples, the properties of the UV-curable resin and the UV-curable coating were tested according to the following methods: resin viscosity was determined using an NDJ-8 rotational viscometer according to GB / T 21059-2007; resin acid value was determined according to GB / T 6743-2008; coating hardness was determined according to GB / T 6739-2006; coating adhesion was measured according to GB-T 9286-1998; water resistance was determined using the room temperature immersion method according to GB / T 5209-1985; alcohol resistance was determined according to GB / T 1763-79; acid / alkali resistance was determined according to GB / T 9274-2009; impact resistance was determined according to GB / T 20624.2-2006; and coating flexibility was determined using a QTY-10A film bending tester according to GB / T 1731-1993.

[0035] Example 1

[0036] (1) Preparation of composite anhydride-modified UV-curable epoxy acrylate: The composite anhydride-modified UV-curable epoxy acrylate resin of this embodiment has the following raw material formulation by mass percentage as shown in Table 1:

[0037] The preparation process of the composite anhydride-modified UV-curable epoxy acrylate in this embodiment is as follows:

[0038] The above-mentioned components—glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (60% wt of the total catalyst), and p-hydroxyanisole (60 wt% of the total polymerization inhibitor)—were added to a four-necked flask equipped with a stirrer, thermometer, and condenser. The temperature was raised to 75°C and maintained for 1 hour. Subsequently, 10 wt% of tetraethylammonium bromide and p-hydroxyanisole were added every hour, and the temperature was gradually raised to 83°C, 90°C, 97°C, and 105°C, finally reaching 120°C and maintaining the reaction temperature for 4-5 hours. The acid value was measured to be below the theoretical value of 3.0 mg KOH / g. The mixture was then cooled and discharged to obtain a composite anhydride-modified UV-curable epoxy acrylate.

[0039] (2) The physical and chemical properties of the composite anhydride modified UV-curable epoxy resin: the appearance is slightly yellow transparent and clear; the acid value is 2.7 mgKOH / g; the viscosity is 124500 mPa·s.

[0040] (3) Preparation of the UV-curable coating:

[0041] The configuration of the UV-curable coating is shown in Table 2 in terms of mass parts:

[0042] The above formula substances are added into a container and dispersed at a low speed of 600 r / min for 10-15 min. After the coating is placed without bubbles, a four-side wet film applicator is used to coat a film on a wood board, a glass board and a tin plate respectively, the film thickness is 25±2 μm, and the film is cured under a UV curing machine with a power of 600 mW / cm 2 , a wavelength of 365 nm, and the film performance is tested. The film performance is shown in Table 3, which is compared with the performance of the same EA resin on the market and the film performance is shown in Table 3.

[0043] (4) Table 3:

[0044] As shown in Table 3, the composite anhydride modified UV-curable epoxy acrylate resin obtained in the application not only has a decreased resin viscosity, a moderate hardness of the cured film, and improved adhesion of the paint film, but also greatly improved flexibility and impact resistance, and excellent chemical resistance.

[0045] Figure 1 is an infrared spectrum of the composite anhydride modified UV-curable epoxy acrylate in Example 1. As shown in the figure, the peak of the epoxy group at 910 cm -1 disappears, the peak of the ester bond at 1719 cm -1 appears, the peak belonging to the hydroxyl group at 3467 cm -1 is enhanced, the characteristic peak of the carbon-carbon double bond at 1607 cm -1 appears, which proves the ring opening of the epoxy resin and the successful grafting of the acrylic acid intermediate, and the characteristic peak of the anhydride carbonyl group at 1760 cm -1 and 1850 cm -1 is not seen in the figure, indicating that the anhydride group also reacts in the process.

[0046] Figure 2 is a nuclear magnetic hydrogen spectrum of the composite anhydride modified UV-curable epoxy acrylate in Example 1, the benzene ring proton peak at 7.7-7.8 ppm on the benzene anhydride, 7.1 ppm and 6.8 ppm belong to the benzene ring proton peak on the epoxy resin, the double bond proton peak of hydroxyethyl acrylate at 5.9-6.3 ppm, the hydroxyl group generated by the esterification reaction of the anhydride and hydroxyethyl acrylate is at 5.4 ppm, the double bond proton peak of maleic anhydride is at 4.8 ppm, the methylene peak on glutaric anhydride and hydroxyethyl acrylate is at 3.7-4.5 ppm, and the above results prove that the anhydride, hydroxyethyl acrylate and acrylic acid are successfully grafted on E51.

[0047] Figure 3 is a gel chromatogram of the composite anhydride modified UV-curable epoxy acrylate in Example 1, and the data of the UV-curable epoxy acrylate obtained in Example 1 can be obtained: the number average molecular weight (Mn) is 1282 g / mol, and the weight average molecular weight (Mw) is 1321 g / mol.

[0048] Figure 4 is a reaction flow diagram and molecular structure formula diagram in Example 1, in which the composite anhydride reacts with hydroxyethyl acrylate to generate a carboxyl-containing intermediate, and then reacts with acrylic acid and epoxy resin E51 to generate ring-opening reaction, the types of anhydride are more, and the molecular structure possibilities generated in the reaction process are more.

[0049] Compared with Comparative Patent 1 (CN102295730A), the resin prepared by the present application has small viscosity, can balance the hardness and flexibility of the coating film, and has low reaction process temperature, simple process and good resin storage stability. Compared with Comparative Patent 2 (CN104558522A), the resin prepared by the present application has uniform components, can coordinate the contradiction between high coating film hardness and high flexibility, and has low resin production cost and simple process.

[0050] Example 2

[0051] (1) Preparation of the composite anhydride modified UV-curable epoxy acrylate: the composite anhydride modified UV-curable epoxy acrylate resin in this example has the raw material formula mass percentage composition as shown in Table 4:

[0052] The preparation process of the composite anhydride modified UV-curable epoxy acrylate in this example is as follows:

[0053] The above-mentioned components of glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (60%wt of the total amount of catalyst), p-hydroxyanisole (60%wt of the total amount of total polymerization inhibitor) were added to a four-necked flask equipped with a stirring paddle, a thermometer, and a condenser tube, heated to 75°C, and kept for 1 h; then 10%wt of tetraethylammonium bromide and p-hydroxyanisole were added every 1 h, and the temperature was gradually increased to 83°C, 90°C, 97°C, 105°C, and finally to 120°C, and then kept for 4-5 h. The acid value was determined to be below 3.0 mgKOH / g, and the temperature was lowered to obtain the modified UV-curable epoxy acrylate.

[0054] (2) The physical and chemical properties of the modified UV-curable epoxy resin with composite anhydride: the appearance is slightly yellow transparent and clear; the acid value is 1.8 mgKOH / g; the viscosity is 118350 mPa·s.

[0055] (3) Preparation of UV-curable coating:

[0056] The configuration of the UV-curable coating is as follows in Table 5 in mass parts:

[0057] The above-mentioned formula substances were added to a container and dispersed at a low speed of 600 r / min for 10-15 min. After the coating was placed without bubbles, a four-sided wet film applicator was used to coat the wood board, glass plate, and tin plate, respectively, with a coating thickness of 25±2 μm, and cured under a UV curing machine with a power of 600 mW / cm 2 , wavelength 365 nm, and the coating performance was tested. The coating performance is shown in Table 6, which is compared with the performance of Example 2 and the same EA resin on the market.

[0058] (4) Table 6:

[0059] Example 3

[0060] (1) Preparation of modified UV-curable epoxy acrylate with composite anhydride: the mass percentage composition of the raw materials of the modified UV-curable epoxy acrylate with composite anhydride in this example is as shown in Table 7:

[0061] The preparation process of the modified UV-curable epoxy acrylate with composite anhydride in this example:

[0062] The above-mentioned components of glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (60%wt of the total amount of catalyst), p-hydroxyanisole (60%wt of the total amount of total polymerization inhibitor) were added to a four-necked flask equipped with a stirring paddle, a thermometer, and a condenser tube, heated to 75°C, and kept for 1 h; then 10%wt of tetraethylammonium bromide and p-hydroxyanisole were added every 1 h, and the temperature was gradually increased to 83°C, 90°C, 97°C, 105°C, and finally to 120°C, and then kept for 4-5 h. The acid value was determined to be below 3.0 mgKOH / g, and the temperature was lowered to obtain the modified UV-curable epoxy acrylate.

[0063] (2) The physical and chemical properties of the modified UV-curable epoxy resin: the appearance is slightly yellow transparent and clear; the acid value is 1.5 mgKOH / g; the viscosity is 115600 mPa·s.

[0064] (3) Preparation of UV-curable coating:

[0065] The configuration of the UV-curable coating is as follows in Table 8 in mass parts:

[0066] The above-mentioned formula substances were added to a container and dispersed at a low speed of 600 r / min for 10-15 min. After the coating was placed without bubbles, a four-sided wet film applicator was used to coat the wood board, glass plate, and tin plate, respectively, with a coating thickness of 25±2 μm, and cured under a UV curing machine with a power of 600 mW / cm 2 , wavelength 365 nm, and the coating performance was tested. The coating performance is shown in Table 9, which is compared with the performance of Example 3 and the same EA resin on the market.

[0067] (4) Table 9:

[0068] Example 4

[0069] (1) Preparation of modified UV-curable epoxy acrylate: the raw material formula of the modified UV-curable epoxy acrylate resin in this example is as shown in Table 10:

[0070] The preparation process of the modified UV-curable epoxy acrylate in this example:

[0071] The above-mentioned components of glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (60% wt of the total amount of catalyst), p-hydroxyanisole (60% wt of the total amount of total polymerization inhibitor) were added to a four-necked flask equipped with a stirring paddle, a thermometer, and a condenser tube, heated to 75°C, and kept for 1 h; then 10% wt of tetraethylammonium bromide and p-hydroxyanisole were added every 1 h, and the temperature was gradually increased to 83°C, 90°C, 97°C, 105°C, and finally to 120°C, and then kept for 4-5 h. The acid value was determined to be below 3.0 mgKOH / g, and the temperature was lowered to discharge the material. A composite anhydride modified UV-curable epoxy acrylate was obtained.

[0072] (2) The physicochemical properties of the composite anhydride modified UV-curable epoxy resin: the appearance was slightly yellow transparent and clear; the acid value was 2.5 mgKOH / g; the viscosity was 143150 mPa·s.

[0073] (3) Preparation of UV-curable coating:

[0074] The configuration of the UV-curable coating is as follows in Table 11 in mass parts:

[0075] The above-mentioned formula substances were added to a container and dispersed at a low speed of 600 r / min for 10-15 min. After the coating was placed without bubbles, a four-sided wet film applicator was used to coat the wood board, glass plate, and tin plate, respectively, with a coating thickness of 25±2 μm, and cured under a UV curing machine with a power of 600 mW / cm 2 , wavelength 365 nm. The coating performance was tested, and the coating performance is shown in Table 12. The performance of the coating was compared with the same EA resin on the market, and the coating performance is shown in Table 12.

[0076] (4) Table 12:

[0077] Example 5

[0078] (1) Preparation of composite anhydride modified UV-curable epoxy acrylate: the mass percentage composition of the raw materials of the composite anhydride modified UV-curable epoxy acrylate resin of this example is as shown in Table 13:

[0079] Preparation process of the composite anhydride modified UV-curable epoxy acrylate of this example:

[0080] The above-mentioned components of glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (60%wt of the total amount of catalyst), p-hydroxyanisole (60%wt of the total amount of total polymerization inhibitor) were added to a four-necked flask equipped with a stirring paddle, a thermometer, and a condenser tube, heated to 75°C, and kept for 1 h; then 10%wt of tetraethylammonium bromide and p-hydroxyanisole were added every 1 h, and the temperature was gradually increased to 83°C, 90°C, 97°C, 105°C, and finally to 120°C, and then kept for 4-5 h. The acid value was determined to be below 3.0 mgKOH / g, and the temperature was lowered to obtain the modified UV-curable epoxy acrylate.

[0081] (2) The physical and chemical properties of the modified UV-curable epoxy resin with composite anhydride: the appearance is slightly yellow transparent and clear; the acid value is 2.7 mgKOH / g; the viscosity is 138550 mPa·s.

[0082] (3) Preparation of UV-curable coating:

[0083] The configuration of the UV-curable coating is as follows in Table 14 by mass fraction:

[0084] The above-mentioned formula substances were added to a container and dispersed at a low speed of 600 r / min for 10-15 min. After the coating was placed without bubbles, a four-sided wet film applicator was used to coat the wood board, glass plate, and tin plate, respectively, with a coating thickness of 25±2 μm, and cured under a UV curing machine with a power of 600 mW / cm 2 , wavelength 365 nm, and the coating performance was tested. The coating performance is shown in Table 15, which is compared with the performance of Example 5 and the same EA resin on the market.

[0085] (4) Table 15:

[0086] Example 6

[0087] (1) Preparation of modified UV-curable epoxy acrylate with composite anhydride: the mass percentage composition of the raw materials of the modified UV-curable epoxy acrylate with composite anhydride in this example is as shown in Table 16:

[0088] The preparation process of the modified UV-curable epoxy acrylate with composite anhydride in this example:

[0089] The above-mentioned components of glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (60%wt of the total amount of catalyst), p-hydroxyanisole (60%wt of the total amount of total polymerization inhibitor) were added to a four-necked flask equipped with a stirring paddle, a thermometer, and a condenser tube, heated to 75°C, and kept for 1 h; then 10%wt of tetraethylammonium bromide and p-hydroxyanisole were added every 1 h, and the temperature was gradually increased to 83°C, 90°C, 97°C, 105°C, and finally to 120°C, and then kept for 4-5 h. The acid value was determined to be below 3.0 mgKOH / g, and the temperature was lowered to obtain the modified UV-curable epoxy acrylate.

[0090] (2) The physical and chemical properties of the modified UV-curable epoxy resin: the appearance is slightly yellow transparent and clear; the acid value is 1.9 mgKOH / g; the viscosity is 134800 mPa·s.

[0091] (3) Preparation of UV-curable coating:

[0092] The configuration of the UV-curable coating is as follows in Table 17 in mass parts:

[0093] The above-mentioned formula substances were added to a container and dispersed at a low speed of 600 r / min for 10-15 min. After the coating was placed without bubbles, a four-sided wet film applicator was used to coat the wood board, glass plate, and tin plate, respectively, with a coating thickness of 25±2 μm, and cured under a UV curing machine with a power of 600 mW / cm 2 , wavelength 365 nm, and the coating performance was tested. The coating performance is shown in Table 18, which is compared with the performance of Example 6 and the same EA resin on the market.

[0094] (4) Table 18:

[0095] Example 7

[0096] (1) Preparation of modified UV-curable epoxy acrylate: a modified UV-curable epoxy acrylate resin, the raw material formula mass percentage composition is as shown in Table 19:

[0097] The preparation process of the modified UV-curable epoxy acrylate in this example:

[0098] The above-mentioned components of glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (60%wt of the total amount of catalyst), p-hydroxyanisole (60%wt of the total amount of total polymerization inhibitor) were added to a four-necked flask equipped with a stirring paddle, a thermometer, and a condenser tube, heated to 75°C, and kept for 1 h; then 10%wt of tetraethylammonium bromide and p-hydroxyanisole were added every 1 h, and the temperature was gradually increased to 83°C, 90°C, 97°C, 105°C, and finally to 120°C, and then kept for 4-5 h. The acid value was determined to be below 3.0 mgKOH / g, and the temperature was lowered to discharge the material. A composite anhydride modified UV-curable epoxy acrylate was obtained.

[0099] (2) The physicochemical properties of the composite anhydride modified UV-curable epoxy resin: the appearance was water-white transparent and clear; the acid value was 2.1 mgKOH / g; the viscosity was 103850 mPa·s.

[0100] (3) Preparation of UV-curable coating:

[0101] The configuration of the UV-curable coating is as follows in Table 20 in mass parts:

[0102] The above-mentioned formula substances were added to a container and dispersed at a low speed of 600 r / min for 10-15 min. After the coating was left to stand without bubbles, a four-sided wet film applicator was used to coat the wood board, glass plate, and tin plate, respectively, with a coating thickness of 25±2 μm, and cured under a UV curing machine with a power of 600 mW / cm 2 , wavelength 365 nm. The coating film performance was tested, and the coating film performance is shown in Table 21. The performance of the coating film was detected and compared with the performance of Example 7 and the same EA resin on the market.

[0103] (4) Table 21:

[0104] Example 8

[0105] (1) Preparation of composite anhydride modified UV-curable epoxy acrylate: the mass percentage composition of the raw materials of the composite anhydride modified UV-curable epoxy acrylate resin of this example is as shown in Table 22:

[0106] Preparation process of the composite anhydride modified UV-curable epoxy acrylate of this example:

[0107] The above-mentioned components of glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (60%wt of the total amount of catalyst), p-hydroxyanisole (60%wt of the total amount of total polymerization inhibitor) were added to a four-necked flask equipped with a stirring paddle, a thermometer, and a condenser tube, heated to 75°C, and kept for 1 h; then 10%wt of tetraethylammonium bromide and p-hydroxyanisole were added every 1 h, and the temperature was gradually increased to 83°C, 90°C, 97°C, 105°C, and finally to 120°C, and then kept for 4-5 h. The acid value was determined to be below 3.0 mgKOH / g, and the temperature was lowered to obtain the modified UV-curable epoxy acrylate.

[0108] (2) The physical and chemical properties of the modified UV-curable epoxy resin with composite anhydride: the appearance is water-white transparent and clear; the acid value is 1.6 mgKOH / g; the viscosity is 101450 mPa·s.

[0109] (3) Preparation of UV-curable coating:

[0110] The configuration of the UV-curable coating is as follows in Table 23 by mass fraction:

[0111] The above-mentioned formula substances were added to a container and dispersed at a low speed of 600 r / min for 10-15 min. After the coating was placed without bubbles, a four-sided wet film applicator was used to coat the wood board, glass plate, and tin plate, respectively, with a coating thickness of 25±2 μm, and cured under a UV curing machine with a power of 600 mW / cm 2 , wavelength 365 nm, and the coating film performance was tested. The coating film performance is shown in Table 24, which is compared with the performance of Example 8 and the same EA resin on the market. The detection of coating film performance is shown in Table 24.

[0112] (4) Table 24:

[0113] Example 9

[0114] (1) Preparation of modified UV-curable epoxy acrylate with composite anhydride: the raw material formula of the modified UV-curable epoxy acrylate with composite anhydride in this example is as shown in Table 25:

[0115] The preparation process of the modified UV-curable epoxy acrylate with composite anhydride in this example:

[0116] The pentanedioic anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (60%wt of the total amount of catalyst), p-hydroxyanisole (60%wt of the total amount of total polymerization inhibitor) were added into a four-necked flask equipped with a stirring paddle, a thermometer, and a condenser, heated to 75°C, and kept for 1h; then 10%wt of tetraethylammonium bromide and p-hydroxyanisole were added every 1h, and the temperature was gradually increased to 83°C, 90°C, 97°C, 105°C, and finally to 120°C, and then kept for 4-5h after the acid value was determined to be below 3.0mgKOH / g, the temperature was lowered and the product was discharged, to obtain a composite anhydride modified UV-curable epoxy acrylate.

[0117] (2) The physicochemical properties of the composite anhydride modified UV-curable epoxy resin: the appearance was water-white transparent and clear; the acid value was 2.0mgKOH / g; the viscosity was 97650mPa·s.

[0118] (3) Preparation of UV-curable coating:

[0119] The configuration of the UV-curable coating is shown in Table 26 below in mass parts:

[0120] The above formula substances were added into a container and dispersed at a low speed of 600r / min for 10-15min. After the coating was left to stand without bubbles, a four-sided wet film applicator was used to coat the wood board, glass plate, and tin plate, respectively, with a coating thickness of 25±2μm, and cured under a UV curing machine with a power of 600mW / cm 2 , wavelength 365nm, and the coating film performance was tested. The coating film performance is shown in Table 27, which was compared with the performance of the same EA resin on the market as Comparative Example 9.

[0121] (4) Table 27:

[0122] In the above examples, the epoxy resin can be one of epoxy resin E51, E44, F44, F51, 170, 128, R-828, S-21, and BD-20.

[0123] In the above examples, the catalyst can be at least one of tetraethylammonium bromide, tetrabutylammonium bromide, N,N-dimethylbenzylamine, and triphenylphosphine.

[0124] In the above examples, the polymerization inhibitor is at least one of p-hydroxyanisole, p-benzoquinone, methylhydroquinone, hydroquinone, and 2,5-dimethylhydroquinone.

[0125] In the above embodiments, the reactive diluent can be one of tripropylene glycol diacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, hexanediol diacrylate, triethylene glycol diacrylate.

[0126] In the above embodiments, the photoinitiator can be at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, 1-hydroxycyclohexyl phenyl ketone.

[0127] The above embodiments are the preferred embodiments of the present application, but the embodiments of the present application are not limited by the above embodiments, and any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present application are equivalent replacement methods and are included in the protection scope of the present application.

Claims

1. A process for the preparation of a complex anhydride modified UV light curable epoxy acrylate characterized in that, The method comprises the following steps: (1) The raw materials are weighed according to the following formulation by weight parts: (2) heating and stirring glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin, part of the catalyst, and part of the polymerization inhibitor to 75-80℃ and keeping for 0.8-1.2h, then increasing the temperature in stages, adding the remaining catalyst and the remaining polymerization inhibitor in batches, finally increasing to 115-125℃ and reacting for 4-5h to obtain the composite anhydride modified UV-curable epoxy acrylate; The weight of the part of the catalyst is 55-65% of the total weight of the catalyst; the weight of the part of the polymerization inhibitor is 55-65% of the total weight of the polymerization inhibitor.

2. The method of making a complex anhydride modified UV photo-curable epoxy acrylate according to claim 1, characterized in that, The epoxy resin is one of epoxy resins E51, E44, F44, F51, 170, 128, R-828, S-21, and BD-20.

3. The method of making a complex anhydride modified UV photo-curable epoxy acrylate according to claim 1, wherein, The catalyst is at least one of tetraethylammonium bromide, tetrabutylammonium bromide, N,N-dimethylbenzylamine, and triphenylphosphine.

4. The method of making a complex anhydride modified UV photo-curable epoxy acrylate according to claim 1, wherein, The polymerization inhibitor is at least one of p-hydroxyanisole, p-benzoquinone, methylhydroquinone, hydroquinone, and 2,5-dimethylhydroquinone.

5. The method of making a complex anhydride modified UV photo-curable epoxy acrylate of claim 1, wherein, The temperature is increased by 8-10℃ every 0.8-1.2h, and the remaining catalyst and the remaining polymerization inhibitor are added in 4-5 batches. The method is used for preparing a coating.

6. A complex anhydride modified UV light curable epoxy acrylate characterized in that, By parts by weight, including:

7. Use of the composite anhydride-modified UV photo-curable epoxy acrylate according to claim 6, characterized in that, The coating comprises 65-87 parts of the composite anhydride modified UV-curable epoxy acrylate, 10-30 parts of an active diluent, and 3-5 parts of a photoinitiator by weight.

8. Use according to claim 7, characterized in that, The active diluent is one of dipropylene glycol diacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, hexanediol diacrylate, and triethylene glycol diacrylate.

9. Use according to claim 8, characterized in that, The photoinitiator is at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and 1-hydroxycyclohexyl phenyl ketone.

10. Use according to claim 8, characterized in that, ​

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