An acrylic monomer, an acrylic resin, a method for preparing the same, a paint, and an application thereof

Abstract

The application provides an acrylic monomer, an acrylic resin and a preparation method, paint and application thereof, and belongs to the technical field of paint. The concept of ionic liquid is introduced into the acrylic monomer, the advantages of the acrylic resin paint and the ionic liquid are combined, a series of ionic liquid functionalized acrylic monomers are designed and synthesized to realize the water-based and environment-friendly purposes. The ionic liquid is a new type of organic salt compound which is not easy to volatilize and is very environment-friendly, so that the prepared acrylic resin can be well dispersed in the water phase. The ionic liquid functional group is connected with an allyl group, crosslinking polymerization can be further carried out, and a crosslinked network structure can be formed in the paint film, so that the paint film is more stable.

Description

Technical Field

[0001] This invention relates to the field of coating technology, and in particular to an acrylic monomer, an acrylic resin, a method for preparing the same, a coating, and its application. Background Technology

[0002] Environmental friendliness has become a perpetual theme in the development of coatings in the 21st century. The coatings market is huge, with wide applications in home decoration, furniture, children's toys, industrial protection, and automobiles. These are products that people come into contact with every day, and the residual organic solvents and other toxic substances in traditional solvent-based coatings will greatly affect human health.

[0003] Water-based coatings use water as a solvent or dispersant, reducing or even eliminating the use of organic solvents, significantly lowering VOC emissions. Furthermore, water-based coatings have lower application requirements, making them highly popular. Acrylic resins refer to homopolymers of acrylates or methacrylates and copolymers with other olefin monomers. Compared to other synthetic polymer resins, acrylic resins have many outstanding advantages, such as excellent light and weather resistance, strong durability under outdoor exposure, resistance to UV radiation (not easily decomposed or yellowed), long-term maintenance of original gloss and color, good heat resistance (decomposes but does not change color at 170℃, and remains unchanged at 230℃ or higher), light color, water-white and transparent, corrosion resistance (good resistance to staining and corrosion from acids, alkalis, salts, greases, detergents, and other chemicals), excellent flexibility, and minimal pigment reactivity. Therefore, they are widely used in the automotive, home appliance, metal furniture, coil manufacturing, instrumentation, construction, textile, wood products, papermaking, and plastics industries.

[0004] However, existing waterborne acrylic resins pose environmental hazards. Summary of the Invention

[0005] In view of this, the purpose of this invention is to provide an acrylic monomer, an acrylic resin, a method for preparing the same, a coating, and its application. The acrylic monomer provided by this invention is green and environmentally friendly.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] This invention provides an acrylic monomer having the structure shown in Formula I:

[0008]

[0009] In Formula I, R represents aryl, benzyl, substituted benzyl, alkenyl, alkynyl, or alkyl chain C. y H 2y+1 , where y is an integer from 0 to 20;

[0010] X1- and X2 - It can be independently a fluoride ion, chloride ion, bromide ion, iodide ion, hexafluorophosphate ion, or nitrate ion.

[0011] Preferably, the acrylic monomer has a structure shown in any one of D1 to D9:

[0012]

[0013] The present invention also provides a method for preparing the acrylic monomer described in the above technical solution, comprising the following steps:

[0014] 3,5-Dibenzylbromo-1-benzyl alcohol, imidazole and anhydrous ethanol were mixed and subjected to a first reflux reaction to give 3,5-dibenzylimidazol-1-benzyl alcohol;

[0015] The 3,5-dibenzylimidazol-1-benzyl alcohol, ethylene bromide and anhydrous ethanol were mixed and subjected to a second reflux reaction to obtain the intermediate compound;

[0016] The intermediate compound, acryloyl chloride, and organic solvent were mixed and subjected to a substitution reaction to obtain an acrylate monomer precursor.

[0017] The acrylate monomer precursor is mixed with a sodium salt and subjected to ion exchange to obtain the acrylic monomer.

[0018] Preferably, the molar ratio of 3,5-dibenzylbromo-1-benzyl alcohol to imidazole is 1:2.

[0019] Preferably, the molar ratio of 3,5-dibenzylimidazol-1-benzyl alcohol to ethylene bromide is 1:2.

[0020] The present invention also provides an acrylic resin having the structure shown in Formula II:

[0021]

[0022] In Formula II, R1, R2, and R3 are independently aryl, benzyl, substituted benzyl, alkenyl, alkynyl, or alkyl chain C. y H 2y+1 , where y is an integer from 0 to 20;

[0023] X1 - X2 - X3 - X4 - X5 - and X6 - Independently, it can be fluoride ion, chloride ion, bromide ion, iodide ion, hexafluorophosphate ion, or nitrate ion;

[0024] n, m, and p are independently 0 to 100.

[0025] Preferably, the acrylic resin has a structure shown in any one of formulas P1 to P9:

[0026]

[0027] The present invention also provides a method for preparing the acrylic resin described in the above technical solution, which is obtained by monomer polymerization, wherein the monomer includes the acrylic monomer described in the above technical solution.

[0028] The present invention also provides a coating comprising the following components in weight percentages:

[0029] The above technical solution comprises 10%–60% acrylic resin, 3%–50% filler, 0.1%–5% defoamer, 0.5%–10% thickener, 20%–70% solvent, and 0.1%–5% photoinitiator, with the sum of the mass percentages of each component being 100%.

[0030] The present invention also provides the application of the coating described in the above technical solution in metal coating.

[0031] This invention provides an acrylic monomer with the structure shown in Formula I. This invention introduces the concept of ionic liquids into acrylic monomers, combining the advantages of both acrylic resin coatings and ionic liquids, and designs and synthesizes a series of acrylic monomers functionalized with ionic liquids to achieve water-based and environmentally friendly properties. Ionic liquids are a new type of non-volatile organic salt compound, which is very environmentally friendly, allowing the prepared acrylic resin to be well dispersed in the aqueous phase. Furthermore, the ionic liquid functional groups are attached with allyl groups, which can also undergo cross-linking polymerization, forming a cross-linked network structure in the coating film, which is more stable. Detailed Implementation

[0032] This invention provides an acrylic monomer having the structure shown in Formula I:

[0033]

[0034] In Formula I, R represents aryl, benzyl, substituted benzyl, alkenyl, alkynyl, or alkyl chain C. y H 2y+1 , where y is an integer from 0 to 20;

[0035] X1 - and X2 - It can be independently a fluoride ion, chloride ion, bromide ion, iodide ion, hexafluorophosphate ion, or nitrate ion.

[0036] In this invention, the acrylic monomer preferably has any one of the structures shown in D1 to D9:

[0037]

[0038] The present invention also provides a method for preparing the acrylic monomer described in the above technical solution, comprising the following steps:

[0039] 3,5-Dibenzylbromo-1-benzyl alcohol, imidazole and anhydrous ethanol were mixed and subjected to a first reflux reaction to give 3,5-dibenzylimidazol-1-benzyl alcohol;

[0040] The 3,5-dibenzylimidazol-1-benzyl alcohol, ethylene bromide and anhydrous ethanol were mixed and subjected to a second reflux reaction to obtain the intermediate compound;

[0041] The intermediate compound, acryloyl chloride, and organic solvent were mixed and subjected to a substitution reaction to obtain an acrylate monomer precursor.

[0042] The acrylate monomer precursor is mixed with a sodium salt and subjected to ion exchange to obtain the acrylic monomer.

[0043] Unless otherwise specified, all raw materials used in this invention are commercially available products in the field.

[0044] In this invention, the principle of the preparation method is shown in the following formula:

[0045]

[0046] In this invention, 3,5-dibenzylbromo-1-benzyl alcohol, imidazole and anhydrous ethanol are mixed and subjected to a first reflux reaction to obtain 3,5-dibenzylimidazol-1-benzyl alcohol.

[0047] In this invention, the molar ratio of 3,5-dibenzylbromo-1-benzyl alcohol to imidazole is preferably 1:2.

[0048] In a specific embodiment of the present invention, it is preferable to dissolve the 3,5-dibenzylbromo-1-benzyl alcohol (A) and imidazole in anhydrous ethanol and reflux for 24 h, then concentrate under reduced pressure to remove the solvent, thereby obtaining the 3,5-dibenzylimidazol-1-benzyl alcohol (C).

[0049] After obtaining 3,5-dibenzylimidazol-1-benzyl alcohol, the present invention mixes the 3,5-dibenzylimidazol-1-benzyl alcohol, ethylene bromide and anhydrous ethanol and carries out a second reflux reaction to obtain an intermediate compound.

[0050] In this invention, the molar ratio of 3,5-dibenzylimidazol-1-benzyl alcohol and ethylene bromide is preferably 1:2.

[0051] In a specific embodiment of the present invention, preferably, the 3,5-dibenzylimidazol-1-benzyl alcohol (C) and ethylene bromide are dissolved in anhydrous ethanol, stirred and refluxed overnight, and the solvent is removed under reduced pressure to obtain the intermediate compound (E).

[0052] After obtaining the intermediate compound, the present invention mixes the intermediate compound, acryloyl chloride and organic solvent to carry out a substitution reaction to obtain an acrylate monomer precursor.

[0053] In this invention, the molar ratio of the intermediate compound to acryloyl chloride is preferably 1:1.

[0054] In this invention, the organic solvent is preferably anhydrous dichloromethane.

[0055] In this invention, the temperature of the substitution reaction is preferably room temperature, and the time is preferably 4 hours.

[0056] In a specific embodiment of the present invention, the intermediate compound (E) and acryloyl chloride are preferably dissolved in anhydrous dichloromethane and stirred at room temperature for 4 hours, and the solvent is removed by vacuum concentration to obtain acrylate monomer precursor D.

[0057] After obtaining the acrylate monomer precursor, the present invention mixes the acrylate monomer precursor with a sodium salt and performs ion exchange to obtain the acrylic monomer.

[0058] In this invention, the ion exchange is preferably carried out in an aqueous solution.

[0059] In this invention, the sodium salt is preferably sodium fluoride, sodium chloride, sodium iodide, sodium hexafluorophosphate, or sodium nitrate.

[0060] The present invention also provides an acrylic resin having the structure shown in Formula II:

[0061]

[0062] In Formula II, R1, R2, and R3 are independently aryl, benzyl, substituted benzyl, alkenyl, alkynyl, or alkyl chain C. y H 2y+1 , where y is an integer from 0 to 20;

[0063] X1 - X2 - X3 - X4 - X5 - and X6 - Independently, it can be fluoride ion, chloride ion, bromide ion, iodide ion, hexafluorophosphate ion, or nitrate ion;

[0064] n, m, and p are independently 0 to 100.

[0065] In this invention, the acrylic resin preferably has a structure shown in any of formulas P1 to P9:

[0066]

[0067] The present invention also provides a method for preparing the acrylic resin described in the above technical solution, which is obtained by monomer polymerization, wherein the monomer includes the acrylic monomer described in the above technical solution.

[0068] In this invention, the polymerization is preferably a monomer self-polymer or copolymer.

[0069] The present invention does not impose any special limitation on the specific method of polymerization, and any method known to those skilled in the art can be used.

[0070] In a specific embodiment of the present invention, the acrylate monomer is preferably dissolved in anhydrous methanol, and the initiator azobisisobutyronitrile (AIBN) is added dropwise while stirring. The mixture is stirred and reacted overnight at 80°C. After the reaction is completed, the solvent is removed by concentration to obtain the acrylic resin.

[0071] The present invention also provides a coating comprising the following components in weight percentages:

[0072] The above technical solution comprises 10%–60% acrylic resin, 3%–50% filler, 0.1%–5% defoamer, 0.5%–10% thickener, 20%–70% solvent, and 0.1%–5% photoinitiator, with the sum of the mass percentages of each component being 100%.

[0073] In this invention, the filler content in the coating is preferably 20% to 50% by mass.

[0074] In this invention, the filler content in the coating is preferably 3% to 30% by mass.

[0075] In this invention, the filler is preferably barium sulfate.

[0076] In this invention, the mass percentage of thickener in the water-based coating is preferably 2.0% to 5%.

[0077] In this invention, the thickener is preferably ViscoPlus 300.

[0078] In this invention, the defoamer content in the water-based coating is preferably 0.2% to 5% by mass.

[0079] In this invention, the defoamer is preferably TEGO-81.

[0080] In this invention, the solvent content in the water-based coating is preferably 33.8% to 40% by mass.

[0081] In this invention, the solvent is preferably water and / or ethanol, and when the solvent is a mixture of water and ethanol, the mass ratio of water to ethanol in the mixture is preferably 28.8:5.

[0082] In this invention, the photoinitiator in the water-based coating is preferably 1% to 3% by mass.

[0083] In this invention, the photoinitiator is preferably 1-hydroxycyclohexylphenyl ketone (Irgacure-184), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Lucirin TPO), or 2-hydroxy-2-methyl-1-phenyl-1-propanone (Darocur1173).

[0084] The present invention also provides the application of the coating described in the above technical solution in metal coating.

[0085] The present invention does not impose any special limitation on the specific method of application, and any method known to those skilled in the art can be used.

[0086] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0087] Example 1: Synthesis of acrylic monomer D-1, the principle of which is shown in the following formula:

[0088]

[0089] 293g (1mol) of 3,5-dibenzylbromo-1-benzyl alcohol (1) and 136g (2mol) of imidazole were dissolved in 1L of anhydrous ethanol and refluxed for 24h. The solvent was removed by concentration under reduced pressure to obtain 214g of 3,5-dibenzylimidazol-1-benzyl alcohol (3). 1 HNMR (500MHz, CDCl3) δ7.74 (s, 2H), 7.10 (dd, J = 15.0, 0.6Hz, 2H), 6.92-6.75 (m, 5H), 5.44 (s, 4H), 4.61 (s, 2H).

[0090] 134.0 g (0.5 mol) of 3,5-dibenzylimidazol-1-benzyl alcohol (3) and 106.9 g (1 mol) of ethylene bromide were dissolved in 500 mL of anhydrous ethanol and stirred under reflux overnight. The solvent was removed under reduced pressure to obtain 189 g of intermediate compound (5). 1H NMR (500MHz, CDCl3) δ6.84(d,J=2.9Hz,2H),6.79(t,J=3.0Hz,1H),6.19(s,2H),5.98(d,J=7.5Hz,2H),5.4 4(s,4H),5.22(d,J=7.5Hz,2H),4.61(s,2H),4.14(s,2H),4.04(d,J=24.7Hz,2H),3.21(d,J=24.9Hz,2H).

[0091] 120 g (0.25 mol) of intermediate compound (5) and 22.5 g (0.25 mol) of acryloyl chloride were dissolved in anhydrous dichloromethane and stirred at room temperature for 4 h. The solvent was removed by concentration under reduced pressure to obtain 129.4 g of the target acrylate monomer compound D-1. 1 H NMR (500MHz, CDCl3) δ6.83(d,J=2.9Hz,1H),6.78(t,J=3.0Hz,1H),6.40(dd,J=19.9,4.5Hz,1H),6.34(s,1H),6.11(dd,J=33.5,19.8Hz ,1H),5.93-5.72(m,2H),5.43(s,2H),5.14(d,J=7.5Hz,1H),5.11(s,1H),4.81(s,1H),3.99(d,J=24.9Hz,1H),3.19(d,J=24.7Hz,1H).

[0092] Example 2: Synthesis of acrylic monomer D-2, the principle of which is shown in the following formula:

[0093]

[0094] 120 g (0.25 mol) of intermediate compound (5) and 26.3 g (0.25 mol) of methacryloyl chloride were dissolved in anhydrous dichloromethane and stirred at room temperature for 4 h. The solvent was removed by concentration under reduced pressure to obtain 126.1 g of the target acrylate monomer compound D-2. 1 HNMR (500MHz, CDCl3) δ6.84 (s, 1H), 6.79 (s, 1H), 6.48 (s, 1H), 6.40 (d, J = 2.7Hz, 1H), 5.84 (s, 1 H),5.44(s,1H),5.21(s,1H),5.12(s,1H),4.57(s,1H),3.99(s,1H),3.20(s,1H),2.01(s,1H).

[0095] Example 3: Synthesis of acrylic acid monomer D-3, the principle of which is shown in the following formula:

[0096]

[0097] 120 g (0.25 mol) of intermediate compound (5) and 29.5 g (0.25 mol) of ethyl acryloyl chloride were dissolved in anhydrous dichloromethane and stirred at room temperature for 4 h. The solvent was removed by concentration under reduced pressure to obtain 124.5 g of the target acrylate monomer compound D-3. 1 HNMR(500MHz, CDCl3) δ6.83(d,J=3.0Hz,1H),6.78(t,J=3.0Hz,1H),6.38(s,1H),6.28(dt,J=4.1,2.0Hz,1H),5.89(d,J=7.5Hz,1H),5.53 -5.28(m,2H),5.22-5.00(m,1H),4.83(s,1H),4.02(d,J=24.7Hz,1H),3.22(d,J=24.7Hz,1H),2.63-2.20(m,1H),1.07(t,J=13.4Hz,1H).

[0098] Example 4: Synthesis of acrylic monomer D-4, the principle of which is shown in the following formula:

[0099]

[0100] 120 g (0.25 mol) of intermediate compound (5) and 33.0 g (0.25 mol) of propylacrylyl chloride were dissolved in anhydrous dichloromethane and stirred at room temperature for 4 h. The solvent was removed by concentration under reduced pressure to obtain 121.5 g of the target acrylate monomer compound D-4. 1 HNMR (500MHz, CDCl3) δ6.84 (d, J=2.9Hz, 2H), 6.79 (t, J=3.0Hz, 1H), 6.29 (dt, J= 4.1,2.0Hz,1H),6.20(s,2H),5.77(d,J=7.5Hz,2H),5.49-5.39(m,5H),5.20(d, J=7.5Hz,2H),5.12(s,2H),4.81(s,2H),4.30(d,J=24.7Hz,2H),3.21(d,J=24.7 Hz,2H),2.41(tt,J=15.6,1.9Hz,2H),1.56-1.25(m,2H),0.94(t,J=13.1Hz,3H).

[0101] Example 5: Synthesis of D-5 of acrylic acid monomers, the principle of which is shown in the following formula:

[0102]

[0103] 120 g (0.25 mol) of intermediate compound (5) and 33.0 g (0.25 mol) of isopropylacrylyl chloride were dissolved in anhydrous dichloromethane and stirred at room temperature for 4 h. The solvent was removed by concentration under reduced pressure to obtain 128.4 g of the target acrylate monomer compound D-5. 1 H NMR(500MHz, CDCl3)δ6.80(d,J=2.9Hz,2H),6.75(t,J=2.9Hz,1H),6.36(s,2H ),6.12(dd,J=4.2,2.0Hz,1H),5.86(d,J=7.5Hz,2H),5.44(dd,J=4.2,2.0Hz,1 H),5.41(s,4H),5.09(s,2H),5.05(d,J=7.4Hz,2H),4.82(s,2H),4.00(d,J=2 4.7Hz,2H),3.39-3.25(m,1H),3.21(d,J=24.7Hz,2H),1.03(d,J=12.8Hz,6H).

[0104] Example 6: Synthesis of D-6 acrylic acid monomer, the principle of which is shown in the following formula:

[0105]

[0106] 120 g (0.25 mol) of intermediate compound (5) and 36.5 g (0.25 mol) of butylacryloyl chloride were dissolved in anhydrous dichloromethane and stirred at room temperature for 4 h. The solvent was removed by concentration under reduced pressure to obtain 126.7 g of the target acrylate monomer compound D-6. 1 HNMR(500MHz, CDCl3)δ6.84(s,2H),6.79(s,1H),6.29(d,J=3.8Hz,3H),5.71(s,2H),5.45(d,J=10.0Hz,5H),5 .13(d,J=9.4Hz,4H),4.80(s,2H),4.18(s,2H),3.21(s,2H),2.41(s,2H),1.33(d,J=45.0Hz,4H),0.93(s,3H).

[0107] Example 7: Synthesis of D-7 acrylic monomer, the principle of which is shown in the following formula:

[0108]

[0109] 120 g (0.25 mol) of intermediate compound (5) and 36.5 g (0.25 mol) of 2-methylpropylacrylyl chloride were dissolved in anhydrous dichloromethane and stirred at room temperature for 4 h. The solvent was removed by concentration under reduced pressure to obtain 131.5 g of the target acrylate monomer compound D-7.1 H NMR (500MHz, CDCl3) δ6.84(s,2H),6.79(s,1H),6.38-6.18(m,3H),5.90(s,2H),5.46(s,1H),5.44(s,4H) ,5.12(s,2H),5.08(s,2H),4.43(s,2H),4.10(s,2H),3.26(s,2H),2.46(s,2H),1.88(s,1H),0.90(s,6H).

[0110] Example 8: Synthesis of D-8 acrylic monomer, the principle of which is shown in the following formula:

[0111]

[0112] 120 g (0.25 mol) of intermediate compound (5) and 36.5 g (0.25 mol) of 1-ethylpropylacrylyl chloride were dissolved in anhydrous dichloromethane and stirred at room temperature for 4 h. The solvent was removed by concentration under reduced pressure to obtain 135.4 g of the target acrylate monomer compound D-8. 1H NMR (500 MHz, CDCl3) δ 6.84 (d, J = 3.0 Hz, 2H), 6.78 (t, J = 3.0 Hz, 1H), 6.27 (s, 2H), 6.16 (dd, J = 4.2, 2.0 Hz, 1H), 5.97 (d, J = 7.5 Hz, 2H), 5.47 (dd, J = 4.2, 2.0 Hz, 1H), 5.44 ( s,4H),5.16(d,J=7.4Hz,2H),5.12(s,2H),4.35(s,2H),4.07(d,J=24.7Hz,2H),3. 24(d,J=24.9Hz,2H),3.00-2.73(m,1H),1.36-1.10(m,4H),0.94(t,J=13.2Hz,6H).

[0113] Example 9: Synthesis of D-9 acrylic acid monomer, the principle of which is shown in the following formula:

[0114]

[0115] 120 g (0.25 mol) of intermediate compound (5) and 43.5 g (0.25 mol) of 3-methylpentylacryloyl chloride were dissolved in anhydrous dichloromethane and stirred at room temperature for 4 h. The solvent was removed by concentration under reduced pressure to obtain 142.5 g of the target acrylate monomer compound D-9. 1H NMR (500MHz, CDCl3) δ6.84(s,2H),6.79(s,1H),6.29(d,J=1.8Hz,3H),5.82(s,2H),5.45(d,J=10.0Hz,5H),5.23(s,2H),5. 12(s,2H),4.44(s,2H),4.04(s,2H),3.24(s,2H),2.32(s,2H),1.54(d,J=10.0Hz,4H),1.31(s,1H),0.90(d,J=35.0Hz,6H).

[0116] Example 10: Synthesis of acrylic resin P-1, the principle of which is shown in the following formula:

[0117]

[0118] 53.4 g (0.1 mol) of acrylate monomer compound (D-1) was dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.5 g AIBN dissolved in 50 mL of methanol) was added dropwise. The reaction was stirred overnight at 80 °C. After the reaction was completed, the solvent was removed by concentration to obtain 51.2 g of the target acrylate resin material P-1. 1 H NMR (500MHz, CDCl3) δ6.81(d,J=3.1Hz,2H),6.76(t,J=3.0Hz,1H),6.25(s,2H),5.85(d,J=7.5Hz,2H),5.42(s,4H),5.18(s,2H),5.12 (d,J=7.5Hz,2H),4.70(s,2H),3.97(d,J=24.7Hz,2H),3.17(d,J=24.7Hz,2H),2.32(dd,J=24.2,23.6Hz,1H),0.97(d,J=23.9Hz,2H).

[0119] Example 11: Synthesis of acrylic resin P-2, the principle of which is shown in the following formula:

[0120]

[0121] 54.8 g (0.1 mol) of acrylate monomer compound (D2) was dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.5 g AIBN dissolved in 50 mL of methanol) was added dropwise. The reaction was stirred overnight at 80 °C. After the reaction was completed, the solvent was removed by concentration to obtain 52.8 g of the target acrylate resin material P-2. 1H NMR (500MHz, CDCl3) δ6.84(d,J=2.9Hz,2H),6.78(t,J=3.0Hz,1H),6.29(s,2H),5.91(d,J=7.5Hz,2H),5.44(s,4H),5.2 0(s,2H),5.15(d,J=7.5Hz,2H),4.64(s,2H),4.01(d,J=24.7Hz,2H),3.20(d,J=24.7Hz,2H),1.06(s,2H),0.96(s,3H).

[0122] Example 12: Synthesis of acrylic resin P-3, the principle of which is shown in the following formula:

[0123]

[0124] 56.2 g (0.1 mol) of acrylate monomer compound (D3) was dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.5 g AIBN dissolved in 50 mL of methanol) was added dropwise. The reaction was stirred overnight at 80 °C. After the reaction was completed, the solvent was removed by concentration to obtain 54.7 g of the target acrylate resin material P-3. 1 H NMR(500MHz, CDCl3)δ6.84(d,J=2.9Hz,2H),6.79(t,J=3.0Hz,1H),6.27(s, 2H),5.83(d,J=7.5Hz,2H),5.44(s,4H),5.21(s,2H),5.04(d,J=7.5Hz,2H), 4.59(s,2H),4.15(d,J=24.7Hz,2H),3.23(d,J=24.7Hz,2H),1.89(q,J=14.4 Hz,1H),1.48(dd,J=28.9,14.4Hz,1H),1.01(s,2H),0.89(t,J=14.5Hz,3H).

[0125] Example 13: Synthesis of acrylic resin P-4, the principle of which is shown in the following formula:

[0126]

[0127] 59.0 g (0.1 mol) of acrylate monomer compound (D7) was dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.5 g AIBN dissolved in 50 mL of methanol) was added dropwise. The reaction was stirred overnight at 80 °C. After the reaction was completed, the solvent was removed by concentration to obtain 57.4 g of the target acrylate resin material P-4. 1H NMR(500MHz, CDCl3) δ6.84(d,J=2.9Hz,2H),6.79(t,J=3.0Hz,1H),6.33(s,2 H),5.68(d,J=7.5Hz,2H),5.44(s,4H),5.22(s,2H),5.06(d,J=7.5Hz,2H),4 .91(s,2H),4.00(d,J=24.7Hz,2H),3.21(d,J=24.9Hz,2H),2.01(d,J=11.0H z,1H),1.73-1.51(m,1H),1.51-1.33(m,1H),1.03-0.83(m,6H),0.80(s,2H).

[0128] Example 14: Synthesis of acrylic resin P-5-1, the principle of which is shown in the following formula:

[0129]

[0130] 26.7 g (0.05 mol) of acrylate monomer compound (D-1) and 27.4 g (0.05 mol) of acrylate monomer compound (D-2) were dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.5 g AIBN dissolved in 50 mL of methanol) was added dropwise. The reaction was stirred overnight at 80 °C. After the reaction was completed, the solvent was removed by concentration to obtain 53.8 g of the target acrylate resin material P-5-1. 1 H NMR(500MHz, CDCl3)δ6.83(d,J=3.0Hz,4H),6.78(t,J=3.0Hz,2H),6.23(s,4H ),5.84(d,J=7.5Hz,4H),5.44(s,8H),5.30(dd,J=18.9,11.4Hz,8H),4.54(s, 4H),4.02(d,J=24.7Hz,4H),3.23(d,J=24.7Hz,4H),2.57-2.35(m,1H),2.28( d,J=13.3Hz,1H),1.87(d,J=13.1Hz,1H),1.40(s,3H),1.22(d,J=14.9Hz,2H).

[0131] Example 15: Synthesis of acrylic resin P-6-1, the principle of which is shown in the following formula:

[0132]

[0133] 27.4 g (0.05 mol) of acrylate monomer compound (D-2) and 28.1 g (0.05 mol) of acrylate monomer compound (D-3) were dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.5 g AIBN dissolved in 50 mL of methanol) was added dropwise. The reaction was stirred overnight at 80 °C. After the reaction was completed, the solvent was removed by concentration to obtain 54.2 g of the target acrylate resin material P-6-1. 1 HNMR(500MHz, CDCl3)δ6.83(s,4H),6.78(s,2H),6.24(s,4H),5.81(s,4H),5.43(s,8H),5.37-5.15(m,8H),4.71(s,4H ),4.01(s,4H),3.22(s,4H),2.11(d,J=30.7Hz,2H),1.90(s,1H),1.61(s,1H),1.33(s,2H),1.07(s,3H),0.89(s,3H).

[0134] Example 16: Synthesis of acrylic resin P-7-1, the principle of which is shown in the following formula:

[0135]

[0136] 27.4 g (0.05 mol) of acrylate monomer compound (D-2) and 29.5 g (0.05 mol) of acrylate monomer compound (D-7) were dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.5 g AIBN dissolved in 50 mL of methanol) was added dropwise. The reaction was stirred at 80 °C overnight. After the reaction was completed, the solvent was removed by concentration to obtain 55.7 g of the target acrylate resin material P-7-1. 1 HNMR (500MHz, CDCl3) δ6.84(s,4H),6.79(s,2H),6.25(s,4H),5.72(s,4H),5.44(s,8H),5.30(d,J=3.2Hz,4H),5.26(s,4H),4.63(s, 4H), 4.01 (s, 4H), 3.23 (s, 4H), 2.67 (s, 1H), 2.02 (s, 1H), 1.89 (s, 1H), 1.56 (d, J = 27.0Hz, 2H), 1.37 (s, 2H), 1.07 (s, 3H), 0.91 (s, 6H).

[0137] Example 17: Synthesis of acrylic resin P-8-1, the principle of which is shown in the following formula:

[0138]

[0139] 16.4 g (0.03 mol) of acrylate monomer compound (D-2), 18.9 g (0.03 mol) of acrylate monomer compound (D-3), and 17.3 g (0.03 mol) of acrylate monomer compound (D-5) were dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.5 g AIBN dissolved in 50 mL of methanol) was added dropwise. The reaction was stirred overnight at 80 °C. After the reaction was completed, the solvent was removed by concentration to obtain 52.7 g of the target acrylate resin material P-8-1. 1 H NMR(500MHz,CDCl3)δ6.84(s,6H),6.79(s,3H),6.22(s,6H),5.76(s,6H),5.44(s,12H),5.33(dd,J=35.9,27.8Hz,12H),4.56(s,6H),3.9 9(s,6H),3.21(s,6H),2.77(d,J=17.5Hz,2H),2.46-2.34(m,3H),1.89(d,J=24.0Hz,2H),1.22(s,2H),1.07(s,3H),0.89(d,J=5.0Hz,9H).

[0140] Example 18: Synthesis of acrylic resin P-9, the principle of which is shown in the following formula:

[0141]

[0142] 16.4 g (0.03 mol) of acrylate monomer compound (D-2), 18.9 g (0.03 mol) of acrylate monomer compound (D-3) and 17.7 g (0.03 mol) of acrylate monomer compound (D-7) were dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.5 g AIBN dissolved in 50 mL of methanol) was added dropwise. The reaction was stirred overnight at 80 °C. After the reaction was completed, the solvent was removed by concentration to obtain 54.8 g of the target acrylate resin material P-9-1. 1H NMR (500MHz, CDCl3) δ6.84(d,J=2.9Hz,6H),6.79(t,J=3.0Hz,3H),6.22(s,6H),5.82(d,J=7 .5Hz,6H),5.44(s,12H),5.28(dd,J=13.9,6.7Hz,12H),4.51(s,6H),3.99(d,J=24.9Hz,6H) ,3.21(d,J=24.7Hz,6H),3.07(s,1H),2.69(s,1H),2.64(s,1H),2.28(dt,J=25.8,24.4Hz,1 H),2.03(s,1H),1.93-1.36(m,5H),1.22(d,J=19.4Hz,1H),1.07(s,3H),0.97-0.80(m,9H).

[0143] Example 19 Coating Formulation 1 is shown in Table 1. The contents in Table 1 are mass contents.

[0144] Table 1. Water-based coating formulation for Formula 1

[0145]

[0146]

[0147] Coating formulations 2 to 9 are the same as formulation 1, except that the acrylic resin P-1 in formulation 1 is replaced with P-2, P-3, P-4, P-5-1, P-6-1, P-7-1, P-8-1 and P-9-1 respectively in formulations 2 to 9.

[0148] Waterborne Coating Performance Testing

[0149] Painting

[0150] Clean the surface of the metal substrate with zirconium salt and deionized water to remove contaminants, and then dry. Spray the substrate surface with coatings formulated from one to nine, heat in a tunnel oven at 200°C for 10 minutes, and then irradiate with UV-LED for 10 minutes to allow it to crosslink and cure.

[0151] The hardness, adhesion, solvent resistance (number of alcohol washes), and VOC emission of the coatings obtained from formulations one through nine were tested, and the results are shown in Table 2. The hardness of the cured film was tested according to GB / T 6739—1996 "Determination of Hardness of Coating Film by Pencil Method", with a test range of 4B to 6H; the adhesion test was conducted according to GB / T 9286—1998; the yellowing resistance test was conducted according to GB-T 9761-2008 "Visual Colorimetry of Paints and Varnishes"; the solvent resistance test was conducted according to Method A (immersion method) of GB 9274—1988 "Determination of Resistance to Liquid Media in Paints and Varnishes"; and the VOC emission test was conducted using GB / T 23986—2009 "Determination of Volatile Organic Compound (VOC) Content in Paints and Varnishes by Gas Chromatography". As shown in Table 2, the acrylic resin prepared by this invention can be well dispersed in the aqueous phase, has low VOC content, and exhibits good stability.

[0152] Table 2 Performance Test Results

[0153]

[0154] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. An acrylic monomer, characterized in that, It has any of the structures shown in D1 to D9: 。 2. The method for preparing acrylic monomer according to claim 1, characterized in that, Includes the following steps: 3,5-Dibenzylbromo-1-benzyl alcohol, imidazole and anhydrous ethanol were mixed and subjected to a first reflux reaction to give 3,5-dibenzylimidazol-1-benzyl alcohol; The 3,5-dibenzylimidazol-1-benzyl alcohol, ethylene bromide and anhydrous ethanol were mixed and subjected to a second reflux reaction to obtain the intermediate compound; The intermediate compound, acryloyl chloride compound, and organic solvent are mixed and subjected to a substitution reaction to obtain an acrylate monomer precursor. The acrylate monomer precursor is mixed with a sodium salt and subjected to ion exchange to obtain the acrylic monomer.

3. The preparation method according to claim 2, characterized in that, The molar ratio of 3,5-dibenzylbromo-1-benzyl alcohol to imidazole is 1:

2.

4. The preparation method according to claim 2, characterized in that, The molar ratio of 3,5-dibenzylimidazol-1-benzyl alcohol to ethylene bromide is 1:

2.

5. An acrylic resin, characterized in that, It has a structure shown in any of the formulas P1 to P9: 。 6. The method for preparing the acrylic resin according to claim 5, characterized in that, It is obtained by polymerization of monomers, wherein the monomers include the acrylic monomers of claim 1.

7. A coating, characterized in that, The components include the following components by mass percentage: The acrylic resin of claim 5 comprises 10% to 60%, filler 3% to 50%, defoamer 0.1% to 5%, thickener 0.5% to 10%, solvent 20% to 70%, and photoinitiator 0.1% to 5%, wherein the sum of the mass percentages of each component is 100%.

8. The application of the coating according to claim 7 in metal coating.

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