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 thereof, a paint and application thereof, and belongs to the technical field of paints.The application provides an acrylic monomer, which combines the advantages of acrylic resin paint and ionic liquid, and designs and synthesizes a series of quaternary ammonium salt-containing ionic liquid functionalized acrylic monomers.The ionic liquid is a new type of organic salt compound which is not easy to volatilize, is very environmentally-friendly, and enables the prepared acrylic resin to be well dispersed in an aqueous phase;the triphenylamine group has strong fluorescence performance;the prepared acrylic monomer has fluorescence performance and can be used as an anti-counterfeiting coating;and the organic silane group can improve the adhesion to glass.

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] Coatings, as a highly dynamic industry within the field of polymer materials, have enjoyed enduring prosperity. With the rapid development of the national economy, the development of multifunctional coatings has attracted widespread attention, such as thermochromic coatings, which change color with temperature. These coatings can be applied to toys, home decoration, anti-counterfeiting, and other fields.

[0003] Acrylic resin refers to homopolymers of acrylates or methacrylates and copolymers with other olefin monomers. Compared with other synthetic polymer resins, acrylic resin has many outstanding advantages, such as excellent light and weather resistance, strong durability under external exposure, resistance to UV radiation (not easily decomposed or yellowed), and the ability to maintain its original luster and color for a long time. It also has good heat resistance, not decomposing or discoloring at 170℃ and remaining unchanged at 230℃ or higher. It is light-colored, water-white and transparent, and corrosion-resistant, exhibiting good resistance to staining and corrosion from acids, alkalis, salts, greases, detergents, and other chemicals. Furthermore, it possesses excellent flexibility and minimal pigment reactivity. Therefore, it has wide applications in industries such as automobiles, home appliances, metal furniture, coil manufacturing, instrumentation, construction, textiles, wood products, papermaking, and plastic products.

[0004] However, waterborne acrylic resins have a high surface free energy, which affects their performance as glass coatings due to poor adhesion to glass. Summary of the Invention

[0005] In view of this, the object of the present invention is to provide an acrylic monomer, an acrylic resin, a method for preparing the same, a coating, and its application. The acrylic resin obtained from the acrylic monomer provided by the present invention has excellent adhesion to glass.

[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, R1, R2, R3, and R5 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;

[0010] R4 is a silane-containing functional group;

[0011] X- It consists of fluoride ions, chloride ions, bromide ions, iodide ions, hexafluorophosphate ions, or nitrate ions.

[0012] Preferably, R4 has the structure shown in Formula II:

[0013]

[0014] In Formula II, R6, R7 and R8 are independently alkyl or alkoxy groups, wherein the length of the carbon chain in the alkyl or alkoxy group is 1 to 10.

[0015] Preferably, R4 has the structure shown in Formula III:

[0016]

[0017] Preferably, the acrylic monomer has the structure shown in A1-9, B1-9, C1-9 or D1-9:

[0018]

[0019]

[0020] The present invention also provides a method for preparing the acrylic monomer described in the above technical solution, comprising the following steps:

[0021] Compounds B and C were mixed with an organic solvent to carry out a first substitution reaction, yielding compound D.

[0022] Compound D was mixed with compound E and subjected to an amination reaction to obtain compound F;

[0023] Compound F and compound G were mixed with an organic solvent to carry out a second substitution reaction to obtain compound H;

[0024] Compound H, compound I, and an organic solvent were mixed and subjected to a third substitution reaction to obtain compound J;

[0025] The compound J and its sodium salt were subjected to ion exchange in water to obtain the acrylic acid monomer;

[0026] The structures of compounds B, C, D, E, G, H, I, and J are shown in the following formulas:

[0027]

[0028] Preferably, the amination reaction is performed at a temperature of 90°C.

[0029] The present invention also provides an acrylic resin obtained by polymerization of monomers, wherein the monomers include the acrylic monomers described in the above technical solution.

[0030] Preferably, the acrylic resin has the structure shown in formulas Y1 to Y9:

[0031]

[0032] In equations Y1 to Y9, n and m are independently 0 to 100.

[0033] The present invention also provides a coating comprising the following components in weight percentages:

[0034] The above technical solution comprises 10%–70% acrylic resin, 5%–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%.

[0035] The present invention also provides the application of the coating described in the above technical solution in glass coating.

[0036] This invention provides an acrylic monomer having the structure shown in Formula I. This invention combines the advantages of acrylic resin coatings and ionic liquids to design and synthesize a series of acrylic monomers functionalized with quaternary ammonium salt ionic liquids. Ionic liquids are a new type of non-volatile organic salt compound, which is very environmentally friendly and allows the prepared acrylic resin to be well dispersed in an aqueous phase. The triphenylamine group has strong fluorescent properties. Using the triphenylamine group as the core, the prepared acrylic monomer has fluorescent properties and can be used as an anti-counterfeiting coating. The organosilicon group can improve the adhesion to glass.

[0037] This invention addresses the problem that waterborne acrylic resins have high surface free energy, resulting in poor adhesion to glass and thus affecting their performance as glass coatings. By simultaneously modifying them with organosilicon alkyl groups and quaternary ammonium salt ionic liquid functional groups, an acrylic monomer with good water-activity and adhesion is obtained. The resulting acrylic resin can be used for coating glass substrates. Detailed Implementation

[0038] This invention provides an acrylic monomer having the structure shown in Formula I:

[0039]

[0040] In Formula I, R1, R2, R3, and R5 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;

[0041] R4 is a silane-containing functional group;

[0042] X -It consists of fluoride ions, chloride ions, bromide ions, iodide ions, hexafluorophosphate ions, or nitrate ions.

[0043] In this invention, R4 preferably has the structure shown in Formula II:

[0044]

[0045] In Formula II, R6, R7 and R8 are independently alkyl or alkoxy groups, wherein the length of the carbon chain in the alkyl or alkoxy group is 1 to 10.

[0046] In this invention, R4 preferably has the structure shown in Formula III:

[0047]

[0048] In this invention, the acrylic monomer preferably has the structure shown in A1-9, B1-9, C1-9, or D1-9:

[0049]

[0050]

[0051]

[0052] The present invention also provides a method for preparing the acrylic monomer described in the above technical solution, comprising the following steps:

[0053] Compounds B and C were mixed with an organic solvent to carry out a first substitution reaction, yielding compound D.

[0054] Compound D was mixed with compound E and subjected to an amination reaction to obtain compound F;

[0055] Compound F and compound G were mixed with an organic solvent to carry out a second substitution reaction to obtain compound H;

[0056] Compound H, compound I, and an organic solvent were mixed and subjected to a third substitution reaction to obtain compound J;

[0057] The compound J and its sodium salt were subjected to ion exchange in water to obtain the acrylic acid monomer;

[0058] The structures of compounds B, C, D, E, G, H, I, and J are shown in the following formulas:

[0059]

[0060] Unless otherwise specified, all raw materials used in this invention are commercially available products in the field.

[0061] In this invention, the raw materials used in the preparation method are shown in the following formula:

[0062]

[0063] In this invention, compound B (tris-(4-hydroxyphenyl)amine), compound C, and an organic solvent are mixed to carry out a first substitution reaction to obtain compound D.

[0064] In this invention, the molar ratio of compound B to C is preferably 1:1.

[0065] In this invention, the organic solvent is preferably dichloromethane.

[0066] In this invention, the preferred ratio of compound B to organic solvent is 1 mol: 2 L.

[0067] In this invention, the first substitution reaction is preferably carried out at room temperature for a period of 24 hours.

[0068] In this invention, the first substitution reaction is preferably carried out in an alkaline environment, which is preferably composed of potassium carbonate, and the molar ratio of compound B to potassium carbonate is preferably 1:1.2.

[0069] In a specific embodiment of the present invention, it is preferable to mix the compound B, potassium carbonate, compound C and dichloromethane, stir at room temperature for 24 hours, detect the completeness of the reaction by thin-layer chromatography, filter, remove the filter residue, wash the organic phase three times with pure water, dry and concentrate to obtain the compound D.

[0070] After obtaining compound D, the present invention mixes compound D with compound E to carry out an amination reaction to obtain compound F.

[0071] In this invention, the temperature of the amination reaction is preferably 90°C.

[0072] In this invention, the molar ratio of compound D to E is preferably 1:1.

[0073] In this invention, the amination reaction is preferably carried out in a solvent, preferably an ethanol-water mixture, wherein the volume ratio of ethanol to water in the ethanol-water mixture is preferably 2:3.

[0074] In a specific embodiment of the present invention, compounds D and E are preferably dissolved in an ethanol-water mixture, reacted overnight at 90°C, and concentrated under reduced pressure to obtain compound F.

[0075] After obtaining compound F, the present invention mixes compound F, compound G and an organic solvent to carry out a second substitution reaction to obtain compound H.

[0076] In this invention, the molar ratio of compound F to G is preferably 1:1.

[0077] In this invention, the organic solvent is preferably dichloromethane.

[0078] In this invention, the preferred ratio of compound F to organic solvent is 1 mol: 2 L.

[0079] In a specific embodiment of the present invention, it is preferable to dissolve the compounds F and G in anhydrous dichloromethane, stir at room temperature for 4 hours, and then concentrate under reduced pressure to remove the solvent to obtain the compound H.

[0080] After obtaining compound H, the present invention mixes compound H, compound I and an organic solvent to carry out a third substitution reaction to obtain compound J.

[0081] In this invention, the molar ratio of compound H to I is preferably 1:1.

[0082] In this invention, the organic solvent is preferably dichloromethane.

[0083] In this invention, the preferred ratio of compound H to organic solvent is 1 mol: 5 L.

[0084] In a specific embodiment of the present invention, it is preferable to dissolve compounds H and I in dichloromethane and stir overnight at room temperature, then concentrate under reduced pressure to remove the solvent, thereby obtaining compound J.

[0085] After obtaining compound J, the present invention performs ion exchange between compound J and sodium salt in water to obtain the acrylic acid monomer.

[0086] The present invention also provides an acrylic resin obtained by polymerization of monomers, wherein the monomers include the acrylic monomers described in the above technical solution.

[0087] The present invention does not impose any special limitation on the specific method of polymerization, and any polymerization method known to those skilled in the art can be used.

[0088] 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.

[0089] In this invention, the acrylic resin preferably has the structure shown in formulas Y1 to Y9:

[0090]

[0091] In equations Y1 to Y9, n and m are independently 0 to 100.

[0092] The present invention also provides a coating comprising the following components in weight percentages:

[0093] The above technical solution comprises 10%–70% acrylic resin, 5%–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%.

[0094] In this invention, the filler content in the coating is preferably 10% to 30% by mass.

[0095] In this invention, the filler is preferably barium sulfate.

[0096] In this invention, the mass percentage of thickener in the water-based coating is preferably 2.5% to 5%.

[0097] In this invention, the thickener is preferably ViscoPlus 300.

[0098] In this invention, the defoamer content in the water-based coating is preferably 0.5% to 5% by mass.

[0099] In this invention, the defoamer is preferably TEGO-81.

[0100] In this invention, the solvent content in the water-based coating is preferably 20% to 40% by mass.

[0101] 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 3:2.

[0102] In this invention, the photoinitiator in the water-based coating is preferably 2% to 3% by mass.

[0103] 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).

[0104] The present invention also provides the application of the coating described in the above technical solution in glass coating.

[0105] 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.

[0106] In this invention, the application preferably includes a curing process, which preferably involves heating in a tunnel oven at 200°C for 10 minutes, followed by UV-LED irradiation for 10 minutes.

[0107] 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.

[0108] Example 1: Synthesis of acrylic monomer A-1, the principle of which is shown in the following formula:

[0109]

[0110] 293.3 g (1 mol) of tris-(4-hydroxyphenyl)amine (1), 166 g (1.2 mol) of potassium carbonate, and 187.8 g (1 mol) of 1,2-dibromoethane were mixed with 2 L of dichloromethane and stirred at room temperature for 24 h. The reaction was confirmed to be complete by thin-layer chromatography. The mixture was filtered to remove the residue. The organic phase was washed three times with pure water and dried to obtain 284.5 g of concentrated intermediate compound (3). 1 H NMR (500MHz, CDCl3) δ7.27-7.10(m,2H),7.07-6.93(m,4H),6.88-6.69(m,6H),4.33(t,J=8.1Hz,2H),3.79(t,J=8.1Hz,2H).

[0111] 200 g (0.5 mol) of intermediate compound (3) and 88.6 g (0.5 mol) of methyl butyl benzylamine (4) were dissolved in 1000 mL of ethanol-water (volume ratio 1:1) mixture and reacted overnight at 90 °C. The mixture was then concentrated under reduced pressure to obtain 173 g of compound (5). 1 HNMR (500MHz, CDCl3) δ7.30-7.10(m,3H),7.08-6.94(m,2H),6.89-6.69(m,3H),5.09(s,1H),4.41(t,J=7. 8Hz,1H),3.84(t,J=7.8Hz,1H),1.80(tt,J=15.6,10.9Hz,1H),1.38-1.11(m,1H),0.89(t,J=13.1Hz,2H).

[0112] 172.8 g (0.3 mol) of intermediate compound (5) and 31.4 g (0.3 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 183.5 g of compound (7).1 HNMR (500MHz, CDCl3) δ7.23(d,J=10.0Hz,5H),7.16(d,J=15.0Hz,4H),7.03(d,J=25.0Hz,4H),6.78(d,J=10.0Hz,4H),6.43( s,1H),6.18(s,1H),5.01(s,2H),4.41(s,2H),3.84(s,2H),3.40(s,2H),2.01(s,3H),1.71(s,2H),1.25(s,2H),0.89(s,3H).

[0113] 64.6 g (0.1 mol) of compound 7 and 21.0 g (0.1 mol) of 3-chloropropylmethyldiethoxysilane were dissolved in 500 mL of dichloromethane and stirred overnight at room temperature. The solvent was removed by concentration under reduced pressure to obtain 75.7 g of the target acrylic monomer compound (A-1). 1 H NMR (500MHz, CDCl3) δ7.19(dd,J=32.5,12.5Hz,11H),7.05(s,2H),6.78(s,4H),6.42(s,1H),6.17(s,1H),4.40(s,2H),4.10(s,2H),3.83( d,J=6.8Hz,6H),3.40(d,J=5.4Hz,5H),2.01(s,3H),1.74(d,J=68.4Hz,4H),1.23(d,J=20.0Hz,8H),0.89(s,3H),0.61(s,2H),0.14(s,3H).

[0114] Example 2: Synthesis of acrylic monomer B-2, the principle of which is shown in the following formula:

[0115]

[0116] 64.6 g (0.1 mol) of compound 7 and 18.2 g (0.1 mol) of 3-chloropropylmethyldimethoxysilane were dissolved in 500 mL of dichloromethane and stirred overnight at room temperature. The solvent was removed by concentration under reduced pressure to obtain 75.7 g of the target acrylic acid monomer compound (B-1). 1H NMR(500MHz,Chloroform)δ7.31-7.09(m,11H),7.09-6.98(m,2H),6.88-6.69(m,4H), 6.41(dq,J=4.0,2.0Hz,1H),6.17(dq,J=4.0,2.0Hz,1H),4.82(s,2H),4.39(t,J=7.6H z,2H),4.19-3.98(m,2H),3.83(t,J=7.6Hz,2H),3.53-3.32(m,8H),3.23(s,3H),2.01 (t,J=2.0Hz,3H),1.88-1.58(m,6H),1.37-1.07(m,5H),0.89(dd,J=13.3,12.8Hz,3H).

[0117] 13 C NMR (125MHz, CDCl3) δ166.30,160.21,149.62,140.83,137.07,133.90,131.88,131.21,128.96,128.32,127.34,126.82,1 26.64,121.69,116.04,69.34,67.01,65.07,64.88,64.06,49.62,49.37,25.47,22.25,21.55,19.10,14.00,2.83,-9.21.

[0118] Example 3: Synthesis of acrylic monomer C-1, the principle of which is shown in the following formula:

[0119]

[0120] 64.6 g (0.1 mol) of compound 7 and 24.0 g (0.1 mol) of 3-chloropropyltriethoxysilane were dissolved in 500 mL of dichloromethane and stirred overnight at room temperature. The solvent was removed by concentration under reduced pressure to obtain 75.7 g of the target acrylic monomer compound (C-1). 1HNMR(500MHz,Chloroform)δ7.30-7.09(m,11H),7.10-6.97(m,2H),6.89-6.66(m,4H ),6.43(dq,J=4.0,2.0Hz,1H),6.18(dq,J=4.0,2.0Hz,1H),4.73(s,2H),4.39(t,J=7 .6Hz,2H),4.20-4.00(m,2H),3.84(t,J=7.6Hz,2H),3.59-3.31(m,8H),3.23(s,3H), 2.01(t,J=2.0Hz,3H),1.90-1.69(m,6H),1.36-1.06(m,11H),0.89(t,J=13.1Hz,3H).

[0121] 13 C NMR (125MHz, CDCl3) δ166.30,160.21,149.62,140.83,137.07,133.90,131.88,13 1.21,128.96,128.32,127.34,126.82,126.64,121.69,116.04,69.34,67.01,65. 0.05 mol of acrylate monomer compound (3-2) was dissolved in 500 mL of anhydrous methanol. With stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.1 g AIBN dissolved in 10 mL methanol) was added dropwise. The reaction was stirred overnight at 85 °C. After the reaction was complete, the solvent was removed by concentration to obtain 38.7 g of the target acrylic isocyanate resin material Y-3-1. 1 HNMR(500MHz, CDCl3)δ7.55-7.35(m,8H),7.30(t,J=12.5Hz,9H),6.14(s,1H),5.74(s,1H),5.45(s,1H),5.21(s,1H),5.14(s,2H),4.56(s, 4H),4.40(s,1H),4.24(d,J=18.0Hz,3H),4.09(s,2H),3.95(s,1H),3 .88-3.69(m,4H),3.17(s,1H),2.25(s,1H),1.70(s,1H),1.26(s,2H).

[0122] Example 4: Synthesis of acrylic monomer D-1, the principle of which is shown in the following formula:

[0123]

[0124] 64.6 g (0.1 mol) of compound 7 and 19.8 g (0.1 mol) of 3-chloropropyltrimethoxysilane were dissolved in 500 mL of dichloromethane and stirred overnight at room temperature. The solvent was removed by concentration under reduced pressure to obtain 75.7 g of the target acrylic monomer compound (D-1). 1 HNMR(500MHz,Chloroform)δ7.29-7.10(m,11H),7.09-6.98(m,2H),6.87-6.67(m,4H), 6.43(dq,J=4.0,2.0Hz,1H),6.18(dq,J=4.0,2.0Hz,1H),4.74(s,2H),4.38(t,J=12.6H z,2H),4.19-4.03(m,2H),3.84(t,J=12.6Hz,2H),3.48-3.34(m,11H),3.31(s,3H),2.0 1(t,J=2.0Hz,3H),1.91-1.65(m,6H),1.36-1.11(m,2H),0.89(dd,J=13.4,12.8Hz,3H).

[0125] 13 C NMR (125MHz, CDCl3) δ166.30,160.21,149.62,140.83,137.07,133.90,131.88,131.21,128.96,128.32,127.34,126.8 2,126.64,121.69,116.04,69.34,67.01,65.07,64.88,64.06,50.78,49.62,25.47,21.55,20.83,19.10,14.00,-0.73.

[0126] Example 5: Synthesis of acrylic resin Y-1, the principle of which is shown in the following formula:

[0127]

[0128] 82.0 g (0.1 mol) of acrylate monomer compound (A-1) was dissolved in 500 mL of anhydrous methanol. Under stirring, an amount of catalytic initiator azobisisobutyronitrile (AIBN) (0.2 g AIBN dissolved in 20 mL of methanol) was added dropwise. The reaction was stirred overnight at 90 °C. After the reaction was completed, the solvent was removed by concentration to obtain 75.6 g of the target acrylate resin material Y-1. 1H NMR(500MHz,Chloroform)δ7.31-7.12(m,11H),7.11-6.93(m,2H),6.84-6.66(m,4H),4.68(s,2H),4.39(t,J=7.6Hz,2H),4.19-4.01 (m,2H),3.83(t,J=7.6Hz,2H),3.62-3.33(m,6H),3.23(s,3H),1.93-1.67(m,6H),1.35-1.13(m,16H),0.89(dd,J=13.4,12.8Hz,3H).

[0129] Example 6: Synthesis of acrylic resin Y-2, the principle of which is shown in the following formula:

[0130]

[0131] 79.1 g (0.1 mol) of acrylate monomer compound (B-1) was dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.2 g AIBN dissolved in 20 mL of methanol) was added dropwise. The reaction was stirred overnight at 90 °C. After the reaction was completed, the solvent was removed by concentration to obtain 71.3 g of the target acrylate resin material Y-2. 1 H NMR(500MHz,Chloroform)δ7.32-7.13(m,11H),7.10-6.91(m,2H),6.87-6.65(m,4H),5.08(s,2H),4.40(t,J=9.3Hz,2H),4.20-3 .96(m,2H),3.84(t,J=9.3Hz,2H),3.47-3.28(m,8H),3.18(s,3H),1.97-1.61(m,6H),1.35-1.10(m,10H),0.89(t,J=13.1Hz,3H).

[0132] Example 7: Synthesis of acrylic resin Y-3, the principle of which is shown in the following formula:

[0133]

[0134] 85.0 g (0.1 mol) of acrylate monomer compound (C-1) was dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.2 g AIBN dissolved in 20 mL of methanol) was added dropwise. The reaction was stirred overnight at 90 °C. After the reaction was completed, the solvent was removed by concentration to obtain 79.4 g of the target acrylate resin material Y-3. 1H NMR(500MHz,Chloroform)δ7.28-7.05(m,11H),7.08-6.92(m,2H),6.83-6.61(m,4H),4.67(s,2H),4.28(t,J=7.7Hz,2H),4 .16-3.98(m,2H),3.82(t,J=7.8Hz,2H),3.63-3.22(m,11H),1.95-1.61(m,6H),1.35-1.07(m,16H),0.88(t,J=13.0Hz,3H).

[0135] Example 8: Synthesis of acrylic resin Y-4, the principle of which is shown in the following formula:

[0136]

[0137] 80.7 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) (0.2 g AIBN dissolved in 20 mL of methanol) was added dropwise. The reaction was stirred overnight at 90 °C. After the reaction was completed, the solvent was removed by concentration to obtain 74.8 g of the target acrylate resin material Y-4. 1 H NMR(500MHz,Chloroform)δ7.19(t,J=15.0Hz,11H),7.04(s,2H),6.77(s,4H),4.62(s,2H),4.37(s,2H),4.10 (s,2H),3.83(s,2H),3.39(d,J=2.0Hz,11H),3.25(s,3H),1.91-1.68(m,6H),1.34-1.13(m,7H),0.89(s,3H).

[0138] Example 9: Synthesis of acrylic resin Y-5 (i.e., Y-5-1), the principle of which is shown in the following formula:

[0139]

[0140] 82.0 g (1.0 mol) of acrylate monomer compound (A-1) and 79.1 g (1.0 mol) of acrylate monomer compound (B-1) were dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.4 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 152.7 g of the target acrylate resin material Y-5-1. 1HNMR(500MHz,Chloroform)δ7.33-7.11(m,22H),7.09-6.92(m,4H),6.85-6.69(m,8H),4.59(s,4H),4.48-4.27(m,4H),4.23-4.00( m,4H),3.89-3.66(m,4H),3.59-3.29(m,14H),3.25(s,6H),2.88(s,1H),1.90-1.48(m,13H),1.37-1.06(m,24H),0.96-0.74(m,6H).

[0141] Example 10: Synthesis of acrylic resin Y-6 (i.e., Y-6-1), the principle of which is shown in the following formula:

[0142]

[0143] 82.0 g (1.0 mol) of acrylate monomer compound (A-1) and 85.0 g (1.0 mol) of acrylate monomer compound (C-1) were dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.4 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 161.5 g of the target acrylate resin material Y-6-1. 1 HNMR(500MHz,Chloroform)δ7.32-7.11(m,22H),7.12-6.94(m,4H),6.84-6.67(m,8H),4.81(s,4H),4.54-4.28(m,4H),4.20-3.97(m,4H), 3.92-3.68(m,4H),3.62-3.33(m,14H),3.27(s,6H),2.61(s,1H),2.2 7(s,1H),1.95-1.55(m,12H),1.42-1.04(m,30H),0.97-0.75(m,6H).

[0144] Example 11: Synthesis of acrylic resin Y-7 (i.e., Y-7-1), the principle of which is shown in the following formula:

[0145]

[0146] 82.0 g (1.0 mol) of acrylate monomer compound (A-1) and 80.7 g (1.0 mol) of acrylate monomer compound (D-1) were dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.4 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 151.8 g of the target acrylate resin material Y-7-1. 1 HNMR(500MHz,Chloroform)δ7.33-7.10(m,4H),7.11-6.93(m,1H),6.87-6.70(m,1H),4.93(s,1H),4.52-4.27(m,1H),4.22 -3.98(m,1H),3.95-3.70(m,1H),3.62-3.28(m,4H),2.51(s,1H),1.97-1.58(m,2H),1.33-1.02(m,4H),0.98-0.75(m,1H).

[0147] Example 12: Synthesis of acrylic resin Y-8 (i.e., Y-8-1), the principle of which is shown in the following formula:

[0148]

[0149] 79.1 g (1.0 mol) of acrylate monomer compound (B-1) and 85.0 g (1.0 mol) of acrylate monomer compound (C-1) were dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.4 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 146.8 g of the target acrylate resin material Y-8-1. 1 H NMR (500MHz, Chloroform) δ7.32-7.11(m,22H),7.06(d,J=7.5Hz,4H),6.79(d,J=7.5Hz,8H),4.97(s,4H),4.38(t,J=4.2Hz,4H),4.17-3.98(m,4H),3.8 4(t,J=4.2Hz,4H),3.50(q,J=11.0Hz,6H),3.44-3.35(m,10H),3.31(s,6H), 2.32(s,1H),1.94-1.59(m,13H),1.34-1.06(m,24H),0.89(t,J=6.6Hz,6H).

[0150] Example 13: Synthesis of acrylic resin Y-9 (i.e., Y-9-1), the principle of which is shown in the following formula:

[0151]

[0152] 85.0 g (1.0 mol) of acrylate monomer compound (C-1) and 80.7 g (1.0 mol) of acrylate monomer compound (D-1) were dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.4 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 154.9 g of the target acrylate resin material Y-9-1. 1 HNMR(500MHz,Chloroform)δ7.31-7.12(m,22H),7.11-6.98(m,4H),6.90-6.68(m,8H),4.89(s,4H),4.47-4.27(m,4H),4.18-4.01( m,4H),3.94-3.73(m,4H),3.62-3.26(m,25H),2.75(s,1H),2.06-1.63(m,13H),1.52(s,2H),1.39-1.09(m,19H),0.99-0.74(m,6H).

[0153] Example 14 Coating Formulation 1 is shown in Table 1. The contents in Table 1 are mass contents.

[0154] Table 1. Water-based coating formulation for Formula 1

[0155]

[0156] Coating formulations 2 to 9 are the same as formulation 1, except that the acrylic resin Y-1 in formulation 2 to 9 is replaced with Y-2 to Y-9 respectively.

[0157] Waterborne Coating Performance Testing

[0158] Painting

[0159] Clean the glass substrate surface with deionized water to remove contaminants and 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.

[0160] 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 / T6739—1996 "Determination of Hardness of Coating Film by Pencil Method", with a test range of 4B to 6H; adhesion was tested according to GB / T 9286—1998; yellowing resistance was tested according to GB-T 9761-2008 "Visual Colorimetry of Paints and Varnishes"; solvent resistance was tested according to Method A (immersion method) of GB 9274—1988 "Determination of Resistance to Liquid Media in Paints and Varnishes"; and VOC emission was tested using GB / T23986—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 and has good adhesion to glass, and can be used for coating glass substrates.

[0161] Table 2 Performance Test Results

[0162]

[0163] 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 a structure shown in any of A1~9, B1~9, C1~9 or D1~9: 。 2. An acrylic resin, characterized in that, It is obtained by polymerization of monomers, wherein the monomers include the acrylic monomers of claim 1.

3. The acrylic resin according to claim 2, characterized in that, It has the structure shown in any of the formulas Y1~7 and Y9: ， In equations Y1~7 and Y9, n and m are independently 0~100.

4. A coating, characterized in that, The components include the following components by mass percentage: The acrylic resin of claim 2 or 3 comprises 10% to 70%, filler 5% 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%.

5. The application of the coating according to claim 4 in glass coating.

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