Acid anhydride modified acrylate monomer as well as preparation method and application thereof

Abstract

The invention discloses an acid anhydride modified acrylate monomer and a preparation method and application thereof, the structure of the acid anhydride modified acrylate monomer is as shown in formula (I): # imgabs0 #, R1 is # imgabs1 #, R2 is # imgabs2 #, R3 and R4 are independently selected from hydrogen or methyl, and R1 and R2 are independently selected from hydrogen or methyl. R5 and R6 are independently selected from hydrogen, methyl or # imgabs3. The molecular structure of the acid anhydride modified acrylate monomer provided by the invention contains an aromatic ring, a plurality of double bonds, a plurality of ether bonds and a plurality of acrylate groups, so that the acid anhydride modified acrylate monomer provided by the invention has relatively high crosslinking density and good curing rate in a UV curing system; and the polyurethane has strong wear resistance, acid resistance, water resistance and the like, and is expected to be well applied to the fields of coatings and inks.

Description

Technical Field

[0001] The invention belongs to the field of photosensitive polymer materials, and in particular relates to an anhydride-modified acrylate monomer and a preparation method and application thereof. Background Art

[0002] Traditional coatings, inks and other composite materials currently on the market usually need to be diluted by adding organic solvents, but organic reagents will evaporate and affect the environment, while monomers can be used as a diluent to participate in the reaction while reducing the viscosity of the system, thereby affecting the performance of the cured film. Therefore, monomers are a relatively important part of material preparation. Different monomers can adjust the properties of the cured film, including but not limited to hardness, weather resistance, chemical resistance, etc. Most of the monomers nowadays are monofunctional and difunctional, with low cross-linking density and poor chemical resistance. A small amount of multifunctional monomers are also put into use, but there are still problems such as excessive rigidity and fragility, large coating shrinkage leading to wrinkles, and poor pigment wettability.

[0003] Click chemistry is a concept of efficient chemical reaction, which has the advantages of high efficiency, few by-products and high yield. Diels-Alder reaction is also a click chemistry reaction, which refers to the cycloaddition reaction between conjugated dienes and dienophiles. The reaction process is highly selective, and the reaction product has a stable cyclohexene structure and no by-products are generated. Nowadays, Diels-Alder reaction has been widely used to synthesize a large number of macromolecular compounds with stable structures such as homopolymers, graft copolymers and star polymers, and is one of the commonly used reactions in modern organic synthesis.

[0004] In order to solve the problems that may occur in the coating, it is necessary to use the Diels-Alder reaction to develop a special monomer to improve the wettability of the coating to the pigment, while also making the prepared coating have the advantages of wear resistance, acid resistance and small shrinkage. Summary of the invention

[0005] In view of the technical problems existing in the prior art, the present invention provides an anhydride-modified acrylate monomer, wherein the molecular structure of the anhydride-modified acrylate monomer contains an aromatic ring, multiple double bonds, multiple ether bonds and multiple acrylate groups, thereby enabling the anhydride-modified acrylate monomer of the present invention to have a higher cross-linking density, a good curing rate, and stronger wear resistance, acid resistance, and water resistance in a UV curing system, and is expected to achieve better application in the fields of coatings and inks.

[0006] The object of the present invention is to provide an anhydride-modified acrylate monomer, the structure of which is shown in formula (I):

[0007]

[0008] Among them, R1 is R2 is R3 and R4 are independently selected from hydrogen or methyl, and R5 and R6 are independently selected from hydrogen, methyl or

[0009] Another object of the present invention is to provide a method for preparing the anhydride-modified acrylate monomer, comprising the following steps:

[0010] S1. Mixing anthracene, maleic anhydride and a solvent, heating the mixture to obtain modified maleic anhydride;

[0011] S2. The modified maleic anhydride, acrylic compound, catalyst, inhibitor and solvent are mixed and heated to react to obtain an anhydride-modified compound;

[0012] S3. Under an inert gas atmosphere, the anhydride-modified compound is mixed with a vinyl ether compound, a catalyst, an inhibitor, and a solvent, and heated to react to obtain an anhydride-modified acrylate monomer;

[0013] The acrylic compound includes at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and pentaerythritol triacrylate;

[0014] The vinyl ether compound includes at least one of diethylene glycol divinyl ether, triethylene glycol divinyl ether and the like.

[0015] In some embodiments of the present invention, in S1, the functional group molar ratio of anthracene to maleic anhydride is 1:1.05-1.15. Functional group refers to a functional group that participates in the reaction.

[0016] In some embodiments of the present invention, in S1, the amount of the solvent used is 600-800% of the total mass of the reaction substrate. The reaction substrates are anthracene and maleic anhydride.

[0017] In some embodiments of the present invention, in S1, the solvent is selected from at least one of toluene and xylene.

[0018] In some embodiments of the present invention, in S1, the temperature of the heating reaction is 100 to 180° C., and the time is 1 to 3 hours.

[0019] In some preferred embodiments of the present invention, in S1, the temperature of the heating reaction is 120-160° C., and the time is 1-2 hours.

[0020] In some embodiments of the present invention, in S2, the catalyst is selected from at least one of triphenylphosphine, tetrabutylammonium bromide, p-toluenesulfonic acid, and zinc oxide.

[0021] In some embodiments of the present invention, in S2, the polymerization inhibitor is selected from at least one of hydroquinone, tert-butylhydroquinone, phenothiazine, p-hydroxyanisole, and 2-tert-butylhydroquinone.

[0022] In some embodiments of the present invention, in S2, the solvent is selected from at least one of diethylene glycol dimethyl ether and butyl acetate.

[0023] In some embodiments of the present invention, in S2, the functional group molar ratio of the acrylic compound to the modified maleic anhydride is 1.01-1.05:1.

[0024] In some embodiments of the present invention, in S2, the amount of the polymerization inhibitor is 1000-4000 ppm of the total mass of the reaction substrate. The reaction substrate is modified maleic anhydride and acrylic acid compound.

[0025] In some embodiments of the present invention, in S2, the amount of the catalyst is 800-2500 ppm of the total mass of the reaction substrate. The reaction substrate is modified maleic anhydride and acrylic acid compound.

[0026] In some embodiments of the present invention, in S2, the amount of the solvent used is 60-100% of the total mass of the reaction substrate. The reaction substrate is modified maleic anhydride and acrylic acid compound.

[0027] In some embodiments of the present invention, in S2, the temperature of the heating reaction is 80-140° C., and the time is 1-5 hours.

[0028] In some preferred embodiments of the present invention, in S2, the temperature of the heating reaction is 90-130° C., and the time is 3-5 hours.

[0029] In some embodiments of the present invention, in S3, the molar ratio of the functional groups of the vinyl ether compound to the anhydride-modified compound is 1 to 2:1.

[0030] In some embodiments of the present invention, in S3, the amount of the polymerization inhibitor is 1000-4000 ppm of the total mass of the reaction substrate. The reaction substrate is a vinyl ether compound and an anhydride-modified compound.

[0031] In some embodiments of the present invention, in S3, the amount of the catalyst is 800-2500 ppm of the total mass of the reaction substrate. The reaction substrate is a vinyl ether compound and an anhydride-modified compound.

[0032] In some embodiments of the present invention, in S3, the amount of the solvent used is 20-60% of the total mass of the reaction substrate. The reaction substrate is a vinyl ether compound and an anhydride-modified compound.

[0033] In some embodiments of the present invention, in S3, the inert gas is at least one of nitrogen and argon.

[0034] In some embodiments of the present invention, in S3, the catalyst is selected from at least one of triphenylphosphine, tetrabutylammonium bromide, p-toluenesulfonic acid, zinc oxide, and Pd catalyst.

[0035] In some embodiments of the present invention, in S3, the polymerization inhibitor is selected from at least one of hydroquinone, tert-butylhydroquinone, phenothiazine, p-hydroxyanisole, and 2-tert-butylhydroquinone.

[0036] In some embodiments of the present invention, in S3, the solvent is selected from at least one of diethylene glycol dimethyl ether, butyl acetate, and ethyl acetate.

[0037] In some embodiments of the present invention, in S3, the temperature of the heating reaction is 50-130° C., and the time is 3-8 hours.

[0038] In some preferred embodiments of the present invention, in S3, the temperature of the heating reaction is 60-120° C., and the time is 3-6 hours.

[0039] Another object of the present invention is to provide the use of the anhydride-modified acrylate monomer or the anhydride-modified acrylate monomer prepared by the preparation method of the anhydride-modified acrylate monomer in the preparation of coatings and inks.

[0040] Compared with the prior art, the present invention has the following beneficial effects:

[0041] The present invention uses anthracene with an aromatic ring as a raw material to react to obtain a multifunctional monomer, which is added to a UV curing system, so that the prepared coating has a higher cross-linking density, a good curing rate, and stronger wear resistance, acid resistance, water resistance and other properties. The shortcomings of the prepared coating such as low cross-linking density, poor stability of the cured film, and poor chemical resistance can be avoided, and it is expected to achieve good application in the fields of coatings and inks. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 This is the H-NMR spectrum of the anhydride-modified acrylic monomer M1.

[0043] Figure 2 This is the H-NMR spectrum of the anhydride-modified acrylic monomer M2.

[0044] Figure 3 This is the H-NMR spectrum of the anhydride-modified acrylic monomer M3.

[0045] Figure 4 This is the H-NMR spectrum of the anhydride-modified acrylic monomer M4.

[0046] Figure 5 This is the H-NMR spectrum of the anhydride-modified acrylic monomer M5. DETAILED DESCRIPTION

[0047] In order to enable those skilled in the art to better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0048] DPHA: dipentaerythritol hexaacrylate, an acrylic monomer from Changxing Materials Industry Co., Ltd.;

[0049] Photoinitiator TPO: diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, purchased from Shanghai Puzhen Biotechnology Co., Ltd.;

[0050] Fluorescent brightener 184: bis(benzoxazolyl) derivative, purchased from Wuhan Yitai Technology Co., Ltd. Shanghai Branch;

[0051] Hyperdispersant 24000: polyester type multi-chain polymer, purchased from Suzhou Huacai New Material Technology Co., Ltd.;

[0052] Inhibitor 510: N-nitroso-N-phenylhydroxylamine aluminum, purchased from Hubei Qianmosheng Biotechnology Co., Ltd.;

[0053] Color paste L5B01: Color paste, purchased from the Import Pigment Sales Department of Shanghai Chemical Light Dyestuff Co., Ltd.;

[0054] Vinyl ester resins are conventionally commercially available;

[0055] The chemical structural formula of the anhydride-modified acrylate monomer M1 is the same as that of the anhydride-modified acrylate monomer M2.

[0056] Example 1

[0057] This embodiment provides an anhydride-modified acrylate monomer M1, and the specific process is as follows:

[0058] S1. (17.83 g, 0.10 mol) anthracene, (10.79 g, 0.11 mol) maleic anhydride and (200 g) xylene were added to a 500 ml four-necked flask, a stirring device and a reflux device were installed, and the mixture was slowly heated to 60 ° C and stirred to make the system uniformly mixed, and then the temperature was raised to 140 ° C ± 2 ° C for insulation reaction for 1 hour, during which samples were taken every 20 minutes and the reaction end point was determined by thin layer chromatography until the fluorescence intensity of the sample under 365 nm ultraviolet irradiation no longer changed, the reaction solution was cooled to room temperature to precipitate the crude product, and then a mixed solvent of diethylene glycol dimethyl ether and petroleum ether was used as a recrystallization solvent for purification, and finally filtered and dried to obtain a white solid, i.e., modified maleic anhydride;

[0059] S2. above-mentioned (27.83g, 0.1mol) modified maleic anhydride, (0.18g, 3000ppm) p-hydroxyanisole and (60g) butyl acetate are successively added into 250ml four-necked flask, stirring device is installed and nitrogen is passed through, slowly heated to 60 ℃ of stirring so that the solid dissolution system is mixed; add (0.12g, 2000ppm) p-toluenesulfonic acid, slowly drip (35.76g, 0.12mol) pentaerythritol triacrylate, the flow addition time is controlled at about 0.5 hour, during which the reaction temperature is controlled at 60 ℃~80 ℃, after the question reaction is no longer exothermic, it is warming up to 110 ℃ ± 2 ℃ and carries out insulation reaction 4 hours, and the acid value is titrated until it no longer changes, and the reaction is stopped, and sodium hydroxide solution is utilized to remove excessive acrylic acid compound, and then the solvent is removed by underpressure distillation after anhydrous magnesium sulfate drying to obtain anhydride modified compound;

[0060] S3. (56.25 g, 0.1 mol) of anhydride-modified compound, (0.14 g, 2000 ppm) of p-hydroxyanisole, (0.07 g, 1000 ppm) of zinc oxide and (20 g) of butyl acetate were mixed and the temperature was controlled at 40°C ± 2°C, nitrogen was passed through, and (17.40 g, 0.11 mol) of diethylene glycol divinyl ether was slowly added dropwise, and the addition time was controlled between 0.5 and 1 hour. During this period, the reaction temperature was controlled at 50°C to 60°C. When the reaction temperature no longer changed, the temperature was raised to 70°C ± 2°C for insulation. When the temperature was kept to an acid value lower than 0.2 mgKOH / g, the reaction was terminated to obtain an anhydride-modified acrylic ester monomer M1, with an acid value of <0.2 mgKOH / g (test standard: GB / T6743-2008) and a viscosity of 8000 cps at 25°C (test standard: GB / T 2794-2013), solid content 72% (baked at 110°C); the structure of the anhydride-modified acrylate monomer M1 is as follows:

[0061]

[0062] The nuclear magnetic hydrogen spectrum of the anhydride-modified acrylic ester monomer M1 is as follows Figure 1 As shown, from Figure 1 It can be seen that the chemical shift at 2.94ppm (a) is the characteristic peak of the methylene connected to the ester group; 3.50ppm (b) is the characteristic peak of the methylene connected to the ether bond; 3.96ppm (d) is the characteristic peak of the methylene between the ester group and the tertiary carbon; 6.12ppm (c) is the characteristic peak of the carbon-carbon double bond.

[0063] Example 2

[0064] This embodiment provides an anhydride-modified acrylate monomer M2, and the specific process is as follows:

[0065] S1. (17.83 g, 0.10 mol) anthracene, (10.79 g, 0.11 mol) maleic anhydride and (200 g) toluene were added to a 500 ml four-necked flask, a stirring device and a reflux device were installed, and the mixture was slowly heated to 60 ° C and stirred to make the system uniformly mixed, and then the temperature was raised to 150 ° C ± 2 ° C for insulation reaction for 1 hour, during which samples were taken every 20 minutes and the reaction end point was determined by thin layer chromatography until the fluorescence intensity of the sample under 365 nm ultraviolet irradiation no longer changed, the reaction solution was cooled to room temperature to precipitate the crude product, and then a mixed solvent of diethylene glycol dimethyl ether and petroleum ether was used as a recrystallization solvent for purification, and finally filtered and dried to obtain a white solid, i.e., modified maleic anhydride;

[0066] S2. The above-mentioned (27.83g, 0.1mol) modified maleic anhydride, (0.18g, 3000ppm) hydroquinone and (60g) butyl acetate were successively added to a 250ml four-necked flask, a stirring device was installed and nitrogen was introduced, and the solid solution system was slowly heated to 60°C and stirred to mix evenly; (0.12g, 2000ppm) p-toluenesulfonic acid was added, and (35.76g, 0.12mol) pentaerythritol triacrylate was slowly added dropwise, and the addition time was controlled at about 0.5 hours, during which the reaction temperature was controlled at 60°C to 80°C, and the reaction was heated to 105°C ± 2°C after the reaction was no longer exothermic, and the reaction was kept warm for 5 hours, and the acid value was titrated until it no longer changed, the reaction was stopped, and the excess acrylic acid compound was removed by sodium hydroxide solution, and then the solvent was removed by vacuum distillation after drying with anhydrous magnesium sulfate to obtain an anhydride modified compound;

[0067] S3. (56.25 g, 0.1 mol) of anhydride-modified compound, (0.14 g, 2000 ppm) of phenothiazine, (0.05 g, 800 ppm) of zinc oxide and (20 g) of ethyl acetate were mixed and the temperature was controlled at 40°C ± 2°C, nitrogen was passed through, and (17.40 g, 0.11 mol) of diethylene glycol divinyl ether was slowly added dropwise, and the addition time was controlled between 0.5 and 1 hour. During this period, the reaction temperature was controlled at 50°C to 60°C. When the reaction temperature no longer changed, the temperature was raised to 80°C ± 2°C for insulation. When the temperature was maintained until the acid value was lower than 0.2 mgKOH / g, the reaction was terminated to obtain anhydride-modified acrylic ester monomer M2, with an acid value of <0.2 mgKOH / g (test standard: GB / T 6743-2008) and a viscosity of 8000 cps at 25°C (test standard: GB / T 2794-2013), solid content 73% (baked at 110°C); the structure of the anhydride-modified acrylate monomer M2 is as follows:

[0068]

[0069] The nuclear magnetic hydrogen spectrum of the anhydride-modified acrylic ester monomer M2 is as follows Figure 2 As shown, from Figure 2 It can be seen that the chemical shift at 2.95ppm (a) is the characteristic peak of the methylene connected to the ester group; 3.52ppm (b) is the characteristic peak of the methylene connected to the ether bond; 3.98ppm (d) is the characteristic peak of the methylene between the ester group and the tertiary carbon; 6.10ppm (c) is the characteristic peak of the carbon-carbon double bond.

[0070] Example 3

[0071] This embodiment provides an anhydride-modified acrylate monomer M3, and the specific process is as follows:

[0072] S1. (17.83 g, 0.10 mol) anthracene, (10.79 g, 0.11 mol) maleic anhydride and (200 g) xylene were added to a 500 ml four-necked flask, a stirring device and a reflux device were installed, and the mixture was slowly heated to 60 ° C and stirred to make the system uniformly mixed, and then the temperature was raised to 140 ° C ± 2 ° C for insulation reaction for 1 hour, during which samples were taken every 20 minutes and the reaction end point was determined by thin layer chromatography until the fluorescence intensity of the sample under 365 nm ultraviolet irradiation no longer changed, the reaction solution was cooled to room temperature to precipitate the crude product, and then a mixed solvent of diethylene glycol dimethyl ether and petroleum ether was used as a recrystallization solvent for purification, and finally filtered and dried to obtain a white solid, i.e., modified maleic anhydride;

[0073] S2. The above-mentioned (27.83g, 0.1mol) modified maleic anhydride, (0.12g, 3000ppm) hydroquinone and (60g) butyl acetate were successively added to a 250ml four-necked flask, a stirring device was installed and nitrogen was introduced, and the solid solution system was slowly heated to 60°C and stirred to mix evenly; (0.04g, 1000ppm) p-toluenesulfonic acid was added, and (13.45g, 0.12mol) hydroxyethyl acrylate was slowly added dropwise, and the addition time was controlled at about 0.5 hours, during which the reaction temperature was controlled at 60°C to 80°C, and the reaction was heated to 105°C ± 2°C after the reaction was no longer exothermic, and the reaction was kept warm for 5 hours, and the acid value was titrated until it no longer changed, the reaction was stopped, and the excess acrylic acid compound was removed by sodium hydroxide solution, and then the solvent was removed by vacuum distillation after drying over anhydrous magnesium sulfate to obtain an anhydride modified compound;

[0074] S3. The above-mentioned (39.44g, 0.1mol) anhydride modified compound, (0.11g, 2000ppm) p-hydroxyanisole, (0.09g, 1600ppm) Pd catalyst and (15g) butyl acetate were mixed and the temperature was controlled at 40°C ± 2°C, nitrogen was passed through, and (17.40g, 0.11mol) diethylene glycol divinyl ether was slowly added dropwise, and the addition time was controlled between 0.5-1 hour, during which the reaction temperature was controlled at 50°C to 60°C. When the reaction temperature no longer changed, the temperature was raised to 80°C ± 2°C for insulation, and the temperature was kept until the acid value was lower than 0.2mgKOH / g, and the reaction was terminated to obtain anhydride modified acrylic ester monomer M3, with an acid value of <0.2mgKOH / g (test standard: GB / T 6743-2008), a viscosity of 5500cps at 25°C (test standard: GB / T 2794-2013), solid content 62% (baked at 110°C); the structure of the anhydride-modified acrylate monomer M3 is as follows:

[0075]

[0076] The hydrogen NMR spectrum of the anhydride-modified acrylic ester monomer M3 is as follows: Figure 3 As shown, from Figure 3 It can be seen that the chemical shift at 2.98 ppm (a) is the characteristic peak of the methyl group connected to the ester group; 6.14 ppm (b) is the characteristic peak of the carbon-carbon double bond; and 3.52 ppm (c) is the characteristic peak of the methylene group connected to the ether bond.

[0077] Example 4

[0078] This embodiment provides an anhydride-modified acrylate monomer M4, and the specific process is as follows:

[0079] S1. (17.83 g, 0.10 mol) anthracene, (10.79 g, 0.11 mol) maleic anhydride and (250 g) xylene were added to a 500 ml four-necked flask, a stirring device and a reflux device were installed, and the mixture was slowly heated to 60 ° C and stirred to make the system uniformly mixed, and then the temperature was raised to 145 ° C ± 2 ° C for insulation reaction for 1.5 hours, during which samples were taken every 30 minutes and the reaction end point was determined by thin layer chromatography until the fluorescence intensity of the sample under 365 nm ultraviolet irradiation no longer changed, the reaction solution was cooled to room temperature to precipitate the crude product, and then a mixed solvent of diethylene glycol dimethyl ether and petroleum ether was used as a recrystallization solvent for purification, and finally filtered and dried to obtain a white solid, i.e., modified maleic anhydride;

[0080] S2. The above-mentioned (27.83 g, 0.1 mol) modified maleic anhydride, (0.12 g, 3000 ppm) phenothiazine and (50 g) butyl acetate were successively added to a 250 ml four-necked flask, a stirring device was installed and nitrogen was introduced, and the solid solution system was slowly heated to 60 ° C and stirred to mix evenly; (0.08 g, 2000 ppm) p-toluenesulfonic acid was added, and (15.62 g, 0.12 mol) hydroxypropyl acrylate was slowly added dropwise, and the addition time was controlled at about 0.5 hours. During this period, the reaction temperature was controlled at 60 ° C to 80 ° C, and the reaction was heated to 110 ° C ± 2 ° C after the reaction was no longer exothermic, and the reaction was kept warm for 4 hours. The acid value was titrated until it no longer changed, and the reaction was stopped. The excess acrylic acid compound was removed by sodium hydroxide solution, and then the solvent was removed by vacuum distillation after drying with anhydrous magnesium sulfate to obtain an anhydride modified compound;

[0081] S3. The above-mentioned (40.84 g, 0.1 mol) anhydride-modified compound, (0.12 g, 2000 ppm) phenothiazine, (0.06 g, 1000 ppm) zinc oxide and (20 g) ethyl acetate were mixed and the temperature was controlled at 40°C ± 2°C, nitrogen was passed through, and (17.40 g, 0.11 mol) diethylene glycol divinyl ether was slowly added dropwise, and the addition time was controlled between 0.5 and 1 hour. During this period, the reaction temperature was controlled at 50°C to 60°C. When the reaction temperature no longer changed, the temperature was raised to 75°C ± 2°C for insulation. When the temperature was kept to an acid value of less than 0.2 mgKOH / g, the reaction was terminated to obtain an anhydride-modified acrylic ester monomer M4, with an acid value of <0.2 mgKOH / g (test standard: GB / T6743-2008) and a viscosity of 6000 cps at 25°C (test standard: GB / T 2794-2013), solid content 65% (baked at 110°C); the structure of the anhydride-modified acrylate monomer M4 is as follows:

[0082]

[0083] The H NMR spectrum of the anhydride-modified acrylic ester monomer M4 is as follows: Figure 4 As shown, from Figure 4 It can be seen that the chemical shift at 2.98ppm (a) is the characteristic peak of the methylene connected to the ester group; 6.12ppm (d) is the characteristic peak of the carbon-carbon double bond; 3.52ppm (c) is the characteristic peak of the methylene connected to the ether bond; 4.08ppm (b) is the characteristic peak of the methylene connected to the ester group.

[0084] Example 5

[0085] This embodiment provides an anhydride-modified acrylate monomer M5, and the specific process is as follows:

[0086] S1. (17.83 g, 0.10 mol) anthracene, (10.79 g, 0.11 mol) maleic anhydride and (200 g) xylene were added to a 500 ml four-necked flask, a stirring device and a reflux device were installed, and the mixture was slowly heated to 60 ° C and stirred to make the system uniformly mixed, and then the temperature was raised to 140 ° C ± 2 ° C for insulation reaction for 1 hour, during which samples were taken every 20 minutes and the reaction end point was determined by thin layer chromatography until the fluorescence intensity of the sample under 365 nm ultraviolet irradiation no longer changed, the reaction solution was cooled to room temperature to precipitate the crude product, and then a mixed solvent of diethylene glycol dimethyl ether and petroleum ether was used as a recrystallization solvent for purification, and finally filtered and dried to obtain a white solid, i.e., modified maleic anhydride;

[0087] S2. above-mentioned (27.83g, 0.1mol) modified maleic anhydride, (0.18g, 3000ppm) p-hydroxyanisole and (60g) butyl acetate are successively added into 250ml four-necked flask, stirring device is installed and nitrogen is passed through, slowly heated to 60 ℃ of stirring so that the solid solution system is mixed; add (0.12g, 2000ppm) p-toluenesulfonic acid, slowly drip (35.76g, 0.12mol) pentaerythritol triacrylate, the flow addition time is controlled at about 0.5 hour, during which the reaction temperature is controlled at 60 ℃~80 ℃, after the reaction is no longer exothermic, it is warming up to 110 ℃ ± 2 ℃ and the reaction is kept warm for 4 hours, the acid value is titrated until it no longer changes, the reaction is stopped, sodium hydroxide solution is utilized to remove excessive acrylic acid compound, and then the solvent is removed by underpressure distillation after anhydrous magnesium sulfate drying to obtain anhydride modified compound;

[0088] S3. The temperature of the above-mentioned (56.25 g, 0.1 mol) anhydride-modified compound, (0.14 g, 1800 ppm) phenothiazine, (0.12 g, 1500 ppm) Pd catalyst and (24 g) butyl acetate was controlled at 40°C ± 2°C, nitrogen was passed through, and (22.25 g, 0.11 mol) triethylene glycol divinyl ether was slowly added dropwise, and the addition time was controlled between 0.5 and 1 hour. During this period, the reaction temperature was controlled at 50°C to 60°C. When the reaction temperature no longer changed, the temperature was raised to 78°C ± 2°C for insulation. When the temperature was kept to an acid value of less than 0.2 mgKOH / g, the reaction was terminated to obtain an anhydride-modified acrylic ester monomer M5, with an acid value of <0.2 mgKOH / g (test standard: GB / T 6743-2008) and a viscosity of 8500 cps at 25°C (test standard: GB / T 2794-2013), solid content 75% (baked at 110°C); the structure of the anhydride-modified acrylate monomer M5 is as follows:

[0089]

[0090] The H NMR spectrum of the anhydride-modified acrylic ester monomer M5 is as follows: Figure 5 As shown, from Figure 5 It can be seen that the chemical shift at 2.96ppm (a) is the characteristic peak of the methylene connected to the ester group; 3.52ppm (b) is the characteristic peak of the methylene connected to the ether bond; 3.98ppm (d) is the characteristic peak of the methylene between the ester group and the tertiary carbon; 6.12ppm (c) is the characteristic peak of the carbon-carbon double bond.

[0091] Example 6

[0092] This embodiment provides a coating, and the specific process is as follows:

[0093] Weigh 8g of vinyl ester resin, 2g of anhydride-modified acrylate monomer M1 and 0.3g of photoinitiator 1173, mix them, stir them evenly in a 65℃ water bath to remove bubbles, and use a 12μm thick wire rod to scrape the coating on the PC board. After standing for 5 minutes, use a mercury lamp to radiate and cure for 10s, with a radiation intensity of 250mJ·cm -2 , to obtain a fully cured coating.

[0094] Examples 7 to 10, Comparative Example 1

[0095] The anhydride-modified acrylate monomer M1 in Example 6 was replaced by anhydride-modified acrylate monomers M2 to M5, respectively, to obtain coatings of Examples 7 to 10; the anhydride-modified acrylate monomer M1 in Example 6 was replaced by acrylic monomer DPHA, to obtain the coating of Comparative Example 1.

[0096] Glass transition temperature Tg test: The instrument mainly uses a differential scanning calorimeter of the NETZSCH DSC3500 model, and the test temperature range is 25℃~300℃. For specific requirements, please refer to GB / T 19466.2-2004 standard. Generally speaking, for coatings, the greater the crosslinking density, the higher the glass transition temperature.

[0097] Chemical solvent resistance test: The PC board with the cured film is immersed in deionized water, 0.05mol / L hydrochloric acid solution, 0.05mol / L sodium hydroxide solution, and anhydrous ethanol respectively, and placed in an oven at 25°C for 12 hours to observe whether the coating shows any loss of gloss, swelling, discoloration, shedding, spots, etc. If these phenomena do not occur, it indicates that the coating is intact and has good chemical solvent resistance, which is represented by 0; if loss of gloss, swelling, discoloration, shedding, spots, etc. occur, it indicates that the coating is damaged, which is represented by Roman numerals 1-5, and the larger the number, the more serious the damage.

[0098] Gloss test: Use a gloss meter of model WGG60-E4 to test the gloss of different coatings at a measuring angle of 60°. The specific operation can be in accordance with GB / T 9754-2007 standard.

[0099] Adhesion test: Adhesion of the coating on the PC board is measured by the cross-cut method. Use a paint film scratch tester to scratch 100 1mm×1mm squares on the coating surface, then stick 3M tape on the coating and press hard, and finally tear off the tape at an angle of 180° to observe whether the coating surface is completely peeled off, the square part is peeled off, and the coating is intact. The adhesion level is 0-5B, and the adhesion is generally required to be greater than or equal to 3B. The specific operation can be in accordance with GB / T 9286-1998 standard.

[0100] Table 1. Coating performance test results of Examples 6 to 10 and Comparative Example 1.

[0101] coating monomer Tg / ℃ Chemical solvent resistance Glossiness Adhesion Example 6 <![CDATA[M1]]> 196 0 74 3B Example 7 <![CDATA[M2]]> 195 0 74 3B Example 8 <![CDATA[M3]]> 185 1 72 2B Example 9 <![CDATA[M4]]> 188 1 73 3B Example 10 <![CDATA[M5]]> 198 0 74 2B Comparative Example 1 DPHA 169 3 72 0B

[0102] As can be seen from Table 1, the anhydride-modified acrylate monomers M1 to M5 of the present invention are used to prepare coatings, and the prepared coatings have high glass transition temperature, good chemical solvent resistance, high gloss and strong adhesion.

[0103] Embodiment 11

[0104] Provide a UV offset red ink, the specific process is as follows:

[0105] Table 2. UV offset red ink formulation.

[0106] Vinyl ester resin 65 Anhydride modified acrylate monomer M1 5 Photoinitiator TPO 3 Fluorescent brightener 184 2 Hyperdispersant 24000 2 Inhibitor 510 0.05 talcum powder 5 Color paste L5B01 18

[0107] Preparation process of UV offset red ink: first, mix the resin, anhydride-modified acrylate monomer M1, inhibitor 510 and photoinitiator TPO in a stirring container to obtain mixed solution A; then place fluorescent brightener 184, superdispersant 24000, talcum powder and color paste L5B01 in another stirrer and mix them to obtain pigment slurry to obtain mixed solution B; then add mixed solution A and mixed solution B to a three-roll grinder for grinding until the ink is smooth and has no granular feeling, and let it stand to defoam. Then use a wire rod with a thickness of 12μm to scrape the ink on the PC board, let it stand for 5 minutes, and then use a mercury lamp to radiate and cure for 30s, with a radiation intensity of 500mJ·cm -2 , you can get a completely cured UV offset red ink.

[0108] Examples 12 to 15 and Comparative Example 2

[0109] The anhydride-modified acrylate monomer M1 in Example 11 was replaced by anhydride-modified acrylate monomers M2 to M5, respectively, to obtain the UV offset red inks of Examples 12 to 15; the anhydride-modified acrylate monomer M1 in Example 11 was replaced by the acrylic monomer DPHA to obtain the UV offset red ink of Comparative Example 2.

[0110] Wettability test: The wettability of the pigment is comprehensively judged by observing the viscosity, ink flying phenomenon, fluidity, glossiness, color density and other factors of the UV offset red ink. The results are expressed in Roman numerals 1-10. The larger the number, the better the wettability of the pigment.

[0111] Table 3. UV offset red ink performance test results of Examples 11 to 15 and Comparative Example 2.

[0112] coating monomer Wettability Embodiment 11 <![CDATA[M1]]> 9 Example 12 <![CDATA[M2]]> 9 Example 13 <![CDATA[M3]]> 7 Embodiment 14 <![CDATA[M4]]> 9 Embodiment 15 <![CDATA[M5]]> 8 Comparative Example 2 DPHA 5

[0113] It can be seen from Table 3 that the anhydride-modified acrylate monomers M1-M5 prepared in Examples 1-5 of the present invention are used to prepare UV offset red ink, and the prepared UV offset red ink has good wettability.

[0114] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in the relevant field should understand that after reading the specification of this application, the technicians can still modify or replace the specific implementation mode of the present invention with equivalents, but these modifications or changes do not deviate from the scope of protection of the pending claims of the present application.

Claims

1. An anhydride-modified acrylate monomer, characterized in that: The structure of the anhydride-modified acrylate monomer is shown in formula (I): Among them, R1 is R2 is R3 and R4 are independently selected from hydrogen or methyl, and R5 and R6 are independently selected from hydrogen, methyl or 2. A method for preparing anhydride-modified acrylate monomers as claimed in claim 1, characterized in that: The steps include: S1. Mixing anthracene, maleic anhydride and a solvent, heating the mixture to obtain modified maleic anhydride; S2. The modified maleic anhydride, acrylic compound, catalyst, inhibitor and solvent are mixed and heated to react to obtain an anhydride-modified compound; S3. Under an inert gas atmosphere, the anhydride-modified compound is mixed with a vinyl ether compound, a catalyst, an inhibitor, and a solvent, and heated to react to obtain an anhydride-modified acrylate monomer; The acrylic compound includes at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and pentaerythritol triacrylate; The vinyl ether compound includes at least one of diethylene glycol divinyl ether, triethylene glycol divinyl ether and the like.

3. The method for preparing anhydride-modified acrylate monomer according to claim 2, characterized in that: In S1, the functional group molar ratio of the anthracene to the maleic anhydride is 1:1.05-1.15; The amount of the solvent used is 600-800% of the total mass of the reaction substrate.

4. The method for preparing anhydride-modified acrylate monomer according to claim 2, characterized in that: In S1, the solvent is selected from at least one of toluene and xylene; The heating reaction is carried out at a temperature of 100 to 180° C. and for a time of 1 to 3 hours.

5. The method for preparing anhydride-modified acrylate monomer according to claim 2, characterized in that: In S2, the catalyst is selected from at least one of triphenylphosphine, tetrabutylammonium bromide, p-toluenesulfonic acid, and zinc oxide; The polymerization inhibitor is selected from at least one of hydroquinone, tert-butylhydroquinone, phenothiazine, p-hydroxyanisole, and 2-tert-butylhydroquinone; The solvent is selected from at least one of diethylene glycol dimethyl ether and butyl acetate.

6. The method for preparing anhydride-modified acrylate monomer according to claim 2, characterized in that: In S2, the functional group molar ratio of the acrylic compound to the modified maleic anhydride is 1.01 to 1.05:1; The dosage of the polymerization inhibitor is 1000-4000ppm of the total mass of the reaction substrate; The amount of the catalyst used is 800 to 2500 ppm of the total mass of the reaction substrate; The amount of the solvent used is 60-100% of the total mass of the reaction substrate.

7. The method for preparing anhydride-modified acrylate monomer according to claim 2, characterized in that: In S2, the heating reaction is carried out at a temperature of 80 to 140°C and for a time of 1 to 5 hours.

8. The method for preparing anhydride-modified acrylate monomer according to claim 2, characterized in that: In S3, the functional group molar ratio of the vinyl ether compound to the anhydride-modified compound is 1 to 2:1; The dosage of the polymerization inhibitor is 1000-4000ppm of the total mass of the reaction substrate; The amount of the catalyst used is 800 to 2500 ppm of the total mass of the reaction substrate; The amount of the solvent used is 20-60% of the total mass of the reaction substrate.

9. The method for preparing anhydride-modified acrylate monomer according to claim 2, characterized in that: In S3, the inert gas is at least one of nitrogen and argon; The catalyst is selected from at least one of triphenylphosphine, tetrabutylammonium bromide, p-toluenesulfonic acid, zinc oxide, and Pd catalyst; The polymerization inhibitor is selected from at least one of hydroquinone, tert-butylhydroquinone, phenothiazine, p-hydroxyanisole, and 2-tert-butylhydroquinone; The solvent is selected from at least one of diethylene glycol dimethyl ether, butyl acetate, and ethyl acetate; The heating reaction is carried out at a temperature of 50 to 130° C. and for a time of 3 to 8 hours.

10. Use of the anhydride-modified acrylate monomer according to claim 1 or the anhydride-modified acrylate monomer prepared by the method for preparing the anhydride-modified acrylate monomer according to any one of claims 2 to 9 in the preparation of coatings and inks.

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