A water-soluble photoinitiator, its preparation method and application

Abstract

The present invention provides a water-soluble photoinitiator, a preparation method thereof and an application thereof, belonging to the technical field of light-curing coating. By introducing ionic liquid groups into epoxy resin-based polymers and polyurethane-based polymers, the present invention can improve the water solubility of epoxy resin-based polymers and polyurethane-based polymers. Using epoxy resin-based polymers and polyurethane-based polymers as the primer and topcoat components of waterborne LED light-curing coatings respectively can effectively improve the hardness, adhesion resistance and solvent resistance of the coatings. By introducing ionic liquid groups into the structure of the photoinitiator, the present invention can improve the water solubility of the photoinitiator. At the same time, the initiator can participate in the curing process as a polymerizable component during the LED light-curing process, and has high anti-migration property, which can effectively improve the safety of waterborne LED light-curing coatings.

Description

[0001] This application is a divisional application of a Chinese patent application filed with the Chinese Patent Office on November 23, 2021, with the application number CN202111591432.0 and the invention title "Aqueous LED Photocurable Coating and Coating Method". Technical Field

[0002] The present invention relates to the technical field of photocurable coating application, and particularly relates to a water-soluble photoinitiator, a preparation method thereof, and an application thereof. Background Art

[0003] With the rapid development of the national economy, China has become the world's largest paint producer and consumer. However, the consumption structure of paints in China is not reasonable. High-pollution solvent-based traditional paints account for a relatively large proportion. Traditional paints use organic solvents as diluents and will release many volatile organic solvents (VOCs), which greatly damage the natural environment on which humans depend for survival. According to statistics, the amount of VOCs released from paint processing and production ranks second only to vehicle exhaust emissions in terms of VOV pollution. With the increasing call for green environmental protection, the research on new environmentally friendly paints such as solvent-free waterborne paints has become a hot topic. Now, waterborne paints are already on the market, but there is still a certain gap in their performance compared with oil-soluble paints. However, the trend of waterborne paints gradually replacing oil-based paints is irresistible, and the research on new high-performance waterborne paints has practical application value.

[0004] As a new surface treatment technology for materials, photocuring technology refers to the process in which monomers or oligomers can undergo polymerization and crosslinking reactions under the irradiation of visible light / ultraviolet light to achieve curing. Photocuring technology has the characteristics of high efficiency, high quality, environmental protection, energy saving, and controllability. The resin used in waterborne photocurable coatings needs to meet the requirement of water solubility, but the water solubility of existing coating resins is often poor, which makes the optional range of water-soluble photocurable resins very limited. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide a water-soluble photoinitiator, a preparation method thereof, and an application thereof. The present invention introduces ionic liquids into waterborne LED photocurable coatings, which can improve the water solubility of polymers used in photocurable coatings and photoinitiators for waterborne LED photocurable coatings.

[0006] The present invention provides the application of ionic liquids in the preparation of waterborne LED-curable coatings. In the present invention, ionic liquid groups are introduced into the structures of polymers for waterborne LED-curable coatings and / or photoinitiators for waterborne LED-curable coatings, obtaining an epoxy resin-based polymer having the structure shown in Formula A, a polyurethane-based polymer having the structure shown in Formula B, and a photoinitiator having the structure shown in Formula C. By introducing ionic liquid groups into the epoxy resin-based polymer and the polyurethane-based polymer, the water solubility of the epoxy resin-based polymer and the polyurethane-based polymer can be improved. Using the epoxy resin-based polymer and the polyurethane-based polymer as the primer and topcoat components of the waterborne LED-curable coating respectively can effectively improve the hardness, adhesion resistance and solvent resistance of the coating. By introducing ionic liquid groups into the structure of the photoinitiator, the water solubility of the photoinitiator can be improved. At the same time, during the LED curing process, the initiator can participate in the curing as a polymerizable component, and it has high anti-migration property, which can effectively improve the safety of the waterborne LED-curable coating. The results of the examples show that the waterborne LED-curable coating prepared using the epoxy resin-based polymer, polyurethane-based polymer and water-soluble photoinitiator of the present invention as raw materials has good hardness, adhesion resistance and solvent resistance, and its VOC release amount is 70-110 mg / mL.

[0007] The present invention provides a coating method for waterborne LED-curable coatings, comprising the following steps: coating a waterborne LED-curable primer coating on the surface of a substrate, and successively performing first UV-LED curing and first drying to obtain a primer film layer; coating a waterborne LED-curable topcoat coating on the surface of the primer film layer, and successively performing second UV-LED curing and second drying to obtain a waterborne LED-curable coating. The waterborne LED-curable coating obtained after coating in the present invention has good hardness, adhesion resistance and solvent resistance. Description of the Drawings

[0008] Figure 1 is the coating process of the waterborne LED-curable coating. Detailed Description of the Invention

[0009] The present invention provides the application of ionic liquids in the preparation of waterborne LED-curable coatings, and the application includes preparing polymers for waterborne LED-curable coatings and / or photoinitiators for waterborne LED-curable coatings.

[0010] The ionic liquid has the structure shown in Formula W:

[0011]

[0012] In Formula W, m is 1-10, preferably 2-8, more preferably 4-6; X is a hydroxyl group or a halogen, and the halogen is preferably Br, Cl or I. In Formula W, the dotted line represents the connection site.

[0013] The present invention provides an epoxy resin-based polymer having the structure shown in Formula I:

[0014]

[0015] In Formula A, R is independently C y H 2y+1 , y is from 0 to 20, preferably from 2 to 15, more preferably from 5 to 10;

[0016] Ar is independently

[0017] m is from 1 to 10, preferably from 2 to 8, more preferably from 4 to 6.

[0018] n is from 2 to 10, preferably from 4 to 8, more preferably from 5 to 6.

[0019] As a specific embodiment of the present invention, the structural formula of the epoxy resin-based polymer preferably has the structure shown in Formula AI, Formula AII, Formula AIII or Formula AIV:

[0020]

[0021]

[0022] The present invention provides a method for preparing the above epoxy resin-based polymer, comprising the following steps:

[0023] The epoxy resin having the structure shown in Formula A-1 reacts with the ionic liquid having the structure shown in Formula b by a substitution reaction to obtain a compound having the structure shown in Formula c;

[0024]

[0025] The compound having the structure shown in Formula A-3 reacts with the compound having the structure shown in Formula A-4 by a ring-opening addition reaction to obtain a compound having the structure shown in Formula A-5;

[0026]

[0027]

[0028] The compound having the structure shown in Formula A-5 reacts with the compound having the structure shown in Formula A-6 by a substitution reaction to obtain the epoxy resin-based polymer having the structure shown in Formula A;

[0029]

[0030] In the present invention, the epoxy resin having the structure shown in Formula A-1 undergoes a substitution reaction with the ionic liquid having the structure shown in Formula A-2 to obtain a compound having the structure shown in Formula A-3.

[0031] In the present invention, the substitution reaction is preferably carried out in an organic solvent, and the organic solvent is preferably dichloromethane, chloroform, toluene, xylene, or chlorobenzene. In the present invention, the substitution reaction is preferably carried out in the presence of a catalyst, and the catalyst is preferably potassium carbonate. In the present invention, the temperature of the substitution reaction is preferably from room temperature to 60 °C, and the time is preferably from 2 to 20 h, more preferably from 5 to 15 h.

[0032] After the substitution reaction, the present invention preferably washes, dries, and removes the organic solvent from the obtained substitution reaction product in sequence.

[0033] After obtaining the compound having the structure shown in Formula A-3, the compound having the structure shown in Formula A-3 undergoes a ring-opening addition reaction with the compound having the structure shown in Formula A-4 to obtain a compound having the structure shown in Formula A-5. In the present invention, the temperature of the ring-opening addition reaction is preferably from room temperature to 100 °C, and the time is preferably from 10 to 36 h, more preferably from 20 to 30 h.

[0034] After obtaining the compound having the structure shown in Formula A-5, the compound having the structure shown in Formula A-5 undergoes a substitution reaction with the compound having the structure shown in Formula A-6 to obtain an epoxy resin-based polymer having the structure shown in Formula A. In the present invention, the substitution reaction is preferably carried out in an organic solvent, and the organic solvent is preferably dichloromethane. In the present invention, the temperature of the substitution reaction is preferably room temperature, and the time is preferably from 0.5 to 5 h, more preferably 2 h.

[0035] The present invention provides the use of the above epoxy resin-based polymer as a polymer for a waterborne LED photocurable primer coating.

[0036] The present invention provides a polyurethane-based polymer having the structure shown in Formula B:

[0037]

[0038] In Formula B, R is independently C y H 2y+1 , y is from 0 to 20, preferably from 2 to 15, and further preferably from 5 to 10.

[0039] A is an aryl group or -(CH2) k -, k is from 2 to 10, preferably from 4 to 8, and more preferably from 5 to 6.

[0040] In the present invention, the preferred aryl group structures are as follows:

[0041]

[0042] m is from 1 to 10, preferably from 2 to 8, more preferably from 4 to 6.

[0043] n is from 2 to 10, preferably from 4 to 8, more preferably from 5 to 6.

[0044] As a specific embodiment of the present invention, the polyurethane-based polymer has a structure shown by formula BI or formula BII:

[0045]

[0046]

[0047] The present invention provides a method for preparing the above polyurethane-based polymer, comprising the following steps:

[0048] A compound having a structure shown by formula B-1 and a compound having a structure shown by formula B-2 are subjected to a nucleophilic addition reaction to obtain a compound having a structure shown by formula B-3;

[0049]

[0050] A compound having a structure shown by formula B-3 and a compound having a structure shown by formula B-4 are subjected to a nucleophilic addition reaction to obtain a compound having a structure shown by formula B-5;

[0051]

[0052] A compound having a structure shown by formula B-5 and an ionic liquid having a structure shown by formula B-6 are subjected to a substitution reaction to obtain a polyurethane-based polymer having a structure shown by formula B;

[0053]

[0054] In the present invention, a compound having a structure shown by formula B-1 and a compound having a structure shown by formula B-2 are subjected to a nucleophilic addition reaction to obtain a compound having a structure shown by formula B-3. In the present invention, the nucleophilic addition reaction is preferably carried out in an organic solvent, and the organic solvent is preferably acetonitrile. In the present invention, the temperature of the reaction is preferably from room temperature to 80 °C, and the time is preferably from 0.5 to 10 h, more preferably from 2 to 5 h.

[0055] After obtaining the compound with the structure shown in Formula B-3, the compound with the structure shown in Formula B-3 and the compound with the structure shown in Formula B-4 are subjected to a nucleophilic addition reaction to obtain a compound with the structure shown in Formula B-5. In the present invention, the reaction is preferably carried out in an organic solvent, and the organic solvent is preferably acetonitrile. In the present invention, the temperature of the reaction is preferably from room temperature to 80 °C, and the time is preferably from 0.5 to 10 hours, more preferably from 2 to 5 h.

[0056] After obtaining the compound with the structure shown in Formula B-5, the compound with the structure shown in Formula B-5 and the ionic liquid with the structure shown in Formula B-6 are subjected to a substitution reaction to obtain a polyurethane-based polymer with the structure shown in Formula B. In the present invention, the substitution reaction is preferably carried out in an organic solvent, and the organic solvent is preferably one or more of dichloromethane, chloroform, toluene, xylene, and chlorobenzene; in the present invention, the temperature of the substitution reaction is preferably from room temperature to 100 °C, and the time is preferably from 10 to 36 h, more preferably 24 h.

[0057] The present invention provides the application of the above polyurethane polymer as a polymer for aqueous LED photocurable topcoat paint.

[0058] The present invention provides a water-soluble photoinitiator having the structure shown in Formula C:

[0059]

[0060] In Formula C, R is independently C y H 2y+1 , y is from 0 to 20, preferably from 2 to 15, more preferably from 5 to 10.

[0061] m is from 0 to 5, preferably from 1 to 4, more preferably from 2 to 3.

[0062] As a specific embodiment of the present invention, the water-soluble photoinitiator has the structure shown in Formula CI or Formula CII:

[0063]

[0064] The present invention provides a preparation method of the above water-soluble photoinitiator, comprising the following steps:

[0065] The compound with the structure shown in Formula C-1 and the compound with the structure shown in Formula C-2 are subjected to a substitution reaction to obtain a compound with the structure shown in Formula C-3;

[0066]

[0067] The compound with the structure shown in Formula C-3 and the compound with the structure shown in Formula C-4 are subjected to a substitution reaction to obtain a compound with the structure shown in Formula C-5;

[0068]

[0069] The compound with the structure shown in Formula C-5 undergoes a substitution reaction with the ionic liquid with the structure shown in Formula C-6 to obtain a photocatalyst with the structure shown in Formula C;

[0070]

[0071] In the present invention, the compound with the structure shown in Formula C-1 undergoes a substitution reaction with the compound with the structure shown in Formula C-2 to obtain a compound with the structure shown in Formula C-3. In the present invention, the substitution reaction is preferably carried out in an organic solvent, and the organic solvent is preferably dichloromethane; in the present invention, the temperature of the substitution reaction is preferably room temperature, and the time is preferably 2 h.

[0072] After obtaining the compound with the structure shown in Formula C-3, the compound with the structure shown in Formula C-3 undergoes a substitution reaction with the compound with the structure shown in Formula C-4 to obtain a compound with the structure shown in Formula C-5. In the present invention, the substitution reaction is preferably carried out in an organic solvent, and the organic solvent is preferably toluene. In the present invention, the temperature of the substitution reaction is preferably 100 °C, and the time is preferably 6 h.

[0073] After obtaining the compound with the structure shown in Formula C-5, the compound with the structure shown in Formula C-5 undergoes a substitution reaction with the ionic liquid with the structure shown in Formula C-6 to obtain a photocatalyst with the structure shown in Formula C. In the present invention, in the present invention, the substitution reaction is preferably carried out in an organic solvent, and the organic solvent is preferably dichloromethane. In the present invention, the substitution reaction is preferably carried out in the presence of a catalyst, and the catalyst is preferably potassium carbonate. In the present invention, the temperature of the substitution reaction is preferably from room temperature to 80 °C, the time is preferably 10 - 36 h, and more preferably 24 h.

[0074] The present invention provides the use of the above water-soluble photoinitiator as a photoinitiator for waterborne LED photocurable coatings.

[0075] The present invention provides a waterborne LED photocurable primer coating, comprising the following components in mass percentage:

[0076]

[0077] The epoxy resin-based polymer is the above epoxy resin-based polymer or the epoxy resin-based polymer prepared by the above preparation method;

[0078] The water-soluble photoinitiator is the above water-soluble photoinitiator or the water-soluble photoinitiator prepared by the above preparation method.

[0079] By mass percentage, the waterborne LED photocurable primer coating provided by the present invention comprises 30-90% of an epoxy resin-based polymer, preferably 40-80%, more preferably 50-70%. In the present invention, the epoxy resin-based polymer has good water solubility.

[0080] By mass percentage, the waterborne LED photocurable primer coating provided by the present invention comprises 0.1-10% of a water-soluble photoinitiator, preferably 0.5-8%, more preferably 1-6%, and further preferably 2-4%. In the present invention, the water-soluble photoinitiator has good water solubility and can participate in curing as a polymerizable component. It has high anti-migration property and can effectively improve the safety of the waterborne LED photocurable coating.

[0081] By mass percentage, the waterborne LED photocurable primer coating provided by the present invention comprises 0.5-20% of an inorganic filler, preferably 1-15%, more preferably 5-10%. In the present invention, the inorganic filler is preferably one or more of calcium carbonate, barium sulfate, talcum powder, kaolin, porous powder quartz, silica, mica powder, wollastonite, bentonite, and attapulgite. In the present invention, the particle size of the inorganic filler is preferably 100-500 nm, more preferably 200-400 nm.

[0082] By mass percentage, the waterborne LED photocurable primer coating provided by the present invention comprises 0.05-2% of an antifoaming agent, preferably 0.1-1.5%, more preferably 0.5-1%. In the present invention, the antifoaming agent is preferably one or more of BYK-011, BYK-012, and TEGO-810.

[0083] By mass percentage, the waterborne LED photocurable primer coating provided by the present invention comprises 0.5-10% of an organic active solvent, preferably 1-8%, more preferably 2-6%, and more preferably 3-5%. In the present invention, the organic active solvent is preferably one or more of dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, and ethanol. In the present invention, the function of the organic active solvent is to improve the processability of the coating so as to facilitate construction during the use of the coating.

[0084] By mass percentage, the waterborne LED photocurable primer coating provided by the present invention comprises 0.5-10% of a thickener, preferably 1-8%, more preferably 2-6%, and more preferably 3-5%. In the present invention, the thickener is preferably one or more of hydroxyethyl cellulose, ethyl acrylate, bentonite, and ViscoPlus3000.

[0085] By mass percentage, the waterborne LED photocurable primer coating provided by the present invention comprises the balance of water.

[0086] The present invention has no special requirements for the preparation method of the water-based LED photocurable primer coating, and it is only necessary to stir the above components evenly.

[0087] The present invention provides a water-based LED photocurable topcoat coating, comprising the following components in mass percentage:

[0088]

[0089] The polyurethane-based polymer is the above polyurethane-based polymer or the polyurethane-based polymer prepared by the above preparation method;

[0090] The water-soluble photoinitiator is the above water-soluble photoinitiator or the water-soluble photoinitiator prepared by the above preparation method.

[0091] In terms of mass percentage, the water-based LED photocurable topcoat coating provided by the present invention comprises 40-80% of polyurethane-based polymer, preferably 60%.

[0092] In terms of mass percentage, the water-based LED photocurable topcoat coating provided by the present invention comprises 0.1-5% of water-soluble photoinitiator, preferably 1.5%.

[0093] In terms of mass percentage, the water-based LED photocurable topcoat coating provided by the present invention comprises 0.1-5% of defoamer, preferably 0.5%. In the present invention, the optional types of the defoamer are the same as those of the defoamer in the water-based LED photocurable primer coating, and will not be elaborated here.

[0094] In terms of mass percentage, the water-based LED photocurable topcoat coating provided by the present invention comprises 1-10% of organic active solvent, preferably 5%. In the present invention, the optional types of the organic active solvent are the same as those of the organic active solvent in the water-based LED photocurable primer coating, and will not be elaborated here.

[0095] In terms of mass percentage, the water-based LED photocurable topcoat coating provided by the present invention comprises 1-10% of thickener, preferably 3%. In the present invention, the optional types of the thickener are the same as those of the thickener in the water-based LED photocurable primer coating, and will not be elaborated here.

[0096] In terms of mass percentage, the water-based LED photocurable topcoat coating provided by the present invention further comprises the balance of water.

[0097] The present invention provides a coating method for water-based LED photocurable coating, comprising the following steps:

[0098] Coat a water-based LED photocurable primer coating on the substrate surface, and successively carry out the first UV LED photocuring and the first drying to obtain a primer film layer;

[0099] Coat a water-based LED photocurable topcoat coating on the surface of the primer film layer, and successively carry out the second UV LED photocuring and the second drying to obtain a water-based LED photocurable coating.

[0100] In the present invention, a water-based LED photocurable primer coating is coated on the substrate surface, and the first UV LED photocuring and the first drying are successively carried out to obtain a primer film layer. In the present invention, the coating method is preferably spraying. The present invention has no special requirements for the spraying method, and the spraying methods well-known to those skilled in the art can be used. In the present invention, the number of coating times is preferably 1 to 3 times, and the coating thickness of the water-based LED photocurable primer coating is preferably 40 to 150 μm, more preferably 60 to 100 μm.

[0101] In the present invention, the temperature of the first UV LED photocuring is preferably room temperature, and the time is preferably 0.5 to 30 min, more preferably 5 to 20 min. In the present invention, the wavelength of the first UV LED photocuring is preferably 320 to 390 nm.

[0102] In the present invention, the first drying preferably includes medium-wave infrared drying and long-wave infrared drying carried out successively. In the present invention, the wavelength of the medium-wave infrared drying is preferably 1.5 to 6 μm, more preferably 2 to 4 μm; the temperature is preferably 80 to 150 °C, more preferably 100 to 120 °C; the time is preferably 10 s to 30 min, more preferably 5 to 20 min.

[0103] In the present invention, the wavelength of the long-wave infrared drying is preferably 6 to 10 μm, more preferably 7 to 9 μm, the temperature is preferably 50 to 300 °C, more preferably 100 to 200 °C, and the time is preferably 1 to 60 min, more preferably 10 to 40 min.

[0104] After obtaining the primer film layer, a water-based LED photocurable topcoat coating is coated on the surface of the primer film layer, and the second UV LED photocuring and the second drying are successively carried out to obtain a water-based LED photocurable coating. In the present invention, the coating method is preferably spraying. The present invention has no special requirements for the spraying method, and the spraying methods well-known to those skilled in the art can be used. In the present invention, the number of coating times is preferably 1 to 3 times, and the coating thickness of the water-based LED photocurable topcoat coating is preferably 20 to 200 μm, more preferably 50 to 150 μm.

[0105] In the present invention, the temperature of the second UVLED photocuring is preferably room temperature, and the time is preferably 0.5 to 30 min, more preferably 5 to 20 min. In the present invention, the wavelength of the second UVLED photocuring is preferably 320 to 390 nm.

[0106] In the present invention, the second drying preferably includes medium-wave infrared drying and long-wave infrared drying carried out in sequence. In the present invention, the wavelength of the medium-wave infrared drying is preferably 1.5 to 6 μm, more preferably 2 to 4 μm; the temperature is preferably 80 to 150 °C, more preferably 100 to 120 °C; the time is preferably 10 s to 30 min, more preferably 5 to 20 min.

[0107] In the present invention, the wavelength of the long-wave infrared drying is preferably 6 to 10 μm, more preferably 7 to 9 μm, the temperature is preferably 50 to 300 °C, more preferably 100 to 200 °C, and the time is preferably 1 to 60 min, more preferably 10 to 40 min.

[0108] In the present invention, the coating process of the waterborne LED photocuring coating is preferably carried out in a dust-free production workshop, and the flowing air is turned on during the coating process; in the present invention, the outlet air of the coating process is preferably sent to a VOC tail gas treatment device for treatment.

[0109] The following is a detailed description of a water-soluble photoinitiator provided by the present invention, its preparation method and application in conjunction with embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0110] Example 1

[0111] Synthesis of epoxy resin-based polymer AI:

[0112] 1.14 kg of bisphenol F epoxy resin (I-1-1) was dissolved in 2 L of dichloromethane, 276 g of anhydrous potassium carbonate was added, and after stirring at room temperature for 1 hour, 788 g of an ionic liquid functional group compound with an alkyl chain (I-1-2) was added. After refluxing for 10 hours, it was cooled to room temperature, washed three times with water, dried over anhydrous sodium sulfate, and concentrated to remove the solvent to obtain an epoxy resin intermediate compound I-1-3 containing an ionic liquid functional group.

[0113] 1 H NMR(500MHz,Chloroform)δ7.06(s,8H),6.82(s,8H),4.42(s,1H),4.26–3.84(m,12H),3.35(d,J=16.1Hz,3H),3.08(d,J=31.9Hz,3H),2.61–2.25(m,6H),2.17(s,1H),1.68–1.03(m,11H).13 C NMR (125 MHz, Common NMR Solvents) δ 173.28, 158.36, 134.24, 131.34, 116.02, 75.03, 70.04, 69.59, 61.02, 54.10, 51.46, 46.51, 42.42, 40.38, 30.13, 27.64, 27.60, 26.58.

[0114] 1.103 kg of intermediate compound (I-1-2) was dissolved in 2 L of anhydrous toluene, 360 g of glacial acetic acid was added to the reaction system, and the mixture was refluxed for 24 hours. After cooling, it was concentrated to obtain epoxy resin I-1-4 containing ionic liquid functional groups and acrylate structural units.

[0115] 1 H NMR (500 MHz, Chloroform) δ 7.08 (s, 8H), 6.84 (s, 8H), 6.39 (d, J = 5.6 Hz, 4H), 6.11 (s, 2H), 5.82 (s, 2H), 4.44 (d, J = 5.5 Hz, 3H), 4.29–3.70 (m, 11H), 3.40 (d, J = 9.6 Hz, 3H), 2.90 (s, 1H), 2.43 (s, 2H), 2.23 (s, 3H), 1.70–1.03 (m, 8H). 13 C NMR (125 MHz, Common NMR Solvents) δ 173.29, 165.14, 158.36, 134.24, 131.34, 129.94, 128.27, 116.02, 89.84, 75.03, 72.30, 70.04, 69.61, 61.01, 54.09, 42.43, 40.38, 30.12, 27.60, 24.40.

[0116] 838 g of epoxy resin I-1-4 containing ionic liquid functional groups and acrylate structural units was dissolved in dry dichloromethane, 180 g of acryloyl chloride was added dropwise at room temperature, and the reaction was carried out at room temperature for two hours. After concentration, acryloyl-capped epoxy resin-based polymer AI was obtained.

[0117] 11H NMR (500 MHz, Chloroform) δ 7.09 (d, J = 7.5 Hz, 8H), 6.85 (d, J = 7.5 Hz, 8H), 6.77–6.66 (m, 2H), 6.41 (dd, J = 10.0, 2.1 Hz, 4H), 6.12 (dd, J = 16.8, 10.0 Hz, 4H), 5.83 (dd, J = 16.8, 2.1 Hz, 4H), 4.60–4.32 (m, 5H), 4.18–3.86 (m, 9H), 3.59 (s, 1H), 3.37 (t, J = 4.8 Hz, 2H), 2.44 (t, J = 5.0 Hz, 2H), 2.08 (s, 1H), 1.62–1.49 (m, 5H), 1.41–1.19 (m, 4H). 13 13C NMR (125 MHz, Common NMR Solvents) δ 173.29, 164.38, 158.36, 134.24, 131.34, 129.94, 128.27, 116.02, 87.19, 75.03, 70.93, 70.04, 69.61, 61.01, 54.09, 42.43, 40.38, 30.12, 27.60, 24.40.

[0118] The synthesis route is as shown in Formula a:

[0119]

[0120] Example 2

[0121] Synthesis of epoxy resin-based polymer AII:

[0122] 1.25 kg of bisphenol A epoxy resin (I-2-1) was dissolved in 2 L of dichloromethane. After adding 276 g of anhydrous potassium carbonate and stirring at room temperature for 1 hour, 788 g of the ionic liquid functional group compound with an alkyl chain (I-2-2) was added. After refluxing for 10 hours, it was cooled to room temperature, washed three times with water, dried over anhydrous sodium sulfate, and concentrated to remove the solvent to obtain the epoxy resin intermediate compound I-2-3 containing an ionic liquid functional group.

[0123] 11H NMR (500 MHz, Chloroform) δ 7.35–7.17 (m, 8H), 6.92–6.73 (m, 8H), 4.41 (tt, J = 12.6, 9.7 Hz, 1H), 4.22–4.03 (m, 6H), 3.96 (dd, J = 24.7, 14.1 Hz, 2H), 3.69 (s, 1H), 3.50 (d, J = 15.6 Hz, 2H), 3.42–3.27 (m, 2H), 3.22–2.93 (m, 2H), 2.59–2.22 (m, 9H), 1.72 (s, 12H), 1.64–1.14 (m, 8H). 13 13C NMR (125 MHz, Common NMR Solvents) δ 173.28, 155.64, 143.67, 129.12, 115.35, 75.03, 70.04, 69.59, 61.02, 54.10, 51.46, 46.51, 45.98, 40.38, 30.26, 30.13, 27.64, 27.60, 26.58.

[0124] 1.36 kg of intermediate compound I-2-3 was dissolved in 2 L of anhydrous toluene, and 288 g of glacial acetic acid was added to the reaction system. The mixture was refluxed for 24 hours, cooled, and concentrated to obtain epoxy resin I-2-4 containing ionic liquid functional groups and acrylate structural units.

[0125] 1 1H NMR (500 MHz, Chloroform) δ 7.33–7.23 (m, 8H), 6.90–6.80 (m, 8H), 6.70–6.62 (m, 2H), 6.41 (dd, J = 19.8, 4.6 Hz, 2H), 6.12 (dd, J = 33.5, 19.8 Hz, 2H), 5.86 (d, J = 4.4 Hz, 1H), 5.79 (d, J = 4.4 Hz, 1H), 4.55–4.37 (m, 3H), 4.28–4.12 (m, 4H), 4.07 (dd, J = 9.4, 0.8 Hz, 2H), 3.41 (dd, J = 18.7, 10.2 Hz, 3H), 3.07 (s, 2H), 2.48–2.40 (m, 2H), 1.77 (s, 3H), 1.72 (s, 12H), 1.60–1.31 (m, 8H), 1.41–1.31 (m, 4H), 1.39–1.26 (m, 4H). 13C NMR (125 MHz, Common NMR Solvents) δ 173.28, 165.14, 155.64, 143.67, 129.94, 129.12, 128.27, 115.35, 89.84, 75.03, 72.30, 70.04, 69.61, 61.02, 54.10, 45.98, 40.38, 30.26, 30.13, 27.60, 24.40.

[0126] 1.04 kg of epoxy resin I-2-4 containing ionic liquid functional groups and acrylate structural units was dissolved in dry dichloromethane, and 180 g of acryloyl chloride was added dropwise at room temperature. The reaction was carried out at room temperature for two hours, and the acryloyl-capped epoxy resin macromolecular material AII was obtained by concentration.

[0127] 1 H NMR (500 MHz, Chloroform) δ 7.28 (d, J = 7.5 Hz, 8H), 6.85 (d, J = 7.5 Hz, 8H), 6.82–6.77 (m, 2H), 6.41 (dd, J = 10.0, 2.1 Hz, 4H), 6.12 (dd, J = 16.8, 10.0 Hz, 4H), 5.83 (dd, J = 16.8, 2.1 Hz, 4H), 4.47 (dd, J = 3.3, 1.9 Hz, 4H), 4.40 (t, J = 4.5 Hz, 1H), 4.08 (dd, J = 9.7, 4.4 Hz, 4H), 3.88 (d, J = 23.4 Hz, 2H), 3.35 (t, J = 7.3 Hz, 2H), 2.55 (s, 1H), 2.44 (t, J = 5.1 Hz, 2H), 2.20 (s, 3H), 1.72 (s, 12H). 13 C NMR (125 MHz, Common NMR Solvents) δ 173.29, 164.38, 155.64, 143.67, 129.94, 129.12, 128.27, 115.35, 87.19, 75.03, 70.93, 70.04, 69.61, 61.01, 54.09, 45.98, 40.38, 30.26, 30.12, 27.60, 24.40.

[0128] The synthesis route is shown in Formula b:

[0129]

[0130] Example 3

[0131] Synthesis of epoxy resin-based polymer AIII:

[0132] 1.41 kg of bisphenol Z epoxy resin (I-3-1) was dissolved in 2 L of dichloromethane. After adding 276 g of anhydrous potassium carbonate and stirring at room temperature for 1 hour, 788 g of an ionic liquid functional group compound with an alkyl chain (I-3-2) was added. After refluxing for 10 hours, it was cooled to room temperature, washed three times with water, dried over anhydrous sodium sulfate, and concentrated to remove the solvent, obtaining an epoxy resin intermediate compound I-3-3 containing an ionic liquid functional group.

[0133] 1 H NMR (500 MHz, Chloroform) δ 7.37–7.18 (m, 8H), 6.92–6.72 (m, 8H), 4.61–4.40 (m, 1H), 4.06 (tdd, J=73.6, 24.8, 14.1 Hz, 8H), 3.52–2.85 (m, 7H), 2.54–2.32 (m, 4H), 2.28–1.76 (m, 11H), 1.67–1.02 (m, 22H). 13 C NMR (125 MHz, Common NMR Solvents) δ 173.28, 155.29, 141.42, 127.58, 116.41, 75.03, 70.04, 69.59, 61.02, 54.10, 51.46, 48.18, 46.51, 40.38, 37.52, 30.13, 27.64, 27.60, 26.58, 25.62, 22.53.

[0134] 1.53 kg of the intermediate compound I-3-3 was dissolved in 2 L of anhydrous toluene. 288 g of glacial acetic acid was added to the reaction system, and the mixture was refluxed for 24 hours, cooled, and concentrated to obtain an epoxy resin I-3-4 containing an ionic liquid functional group and acrylate structural units.

[0135] 1 H NMR (500 MHz, Chloroform) δ 7.39–7.18 (m, 8H), 7.02–6.73 (m, 8H), 6.48–6.31 (m, 4H), 6.12 (dd, J=33.5, 19.8 Hz, 2H), 5.83 (dd, J=33.5, 4.4 Hz, 2H), 4.60–4.35 (m, 3H), 4.26–4.00 (m, 6H), 3.42 (dd, J=39.2, 26.2 Hz, 3H), 2.79 (d, J=61.4 Hz, 2H), 2.50–1.79 (m, 13H), 1.70–0.97 (m, 20H). 13C NMR (125 MHz, Common NMR Solvents) δ 173.29, 165.14, 155.29, 141.41, 129.94, 128.27, 127.57, 116.41, 89.84, 75.03, 72.30, 70.04, 69.61, 61.01, 54.09, 48.17, 40.38, 37.52, 30.12, 27.60, 25.61, 24.40, 22.52.

[0136] 1.12 kg of epoxy resin I-3-4 containing ionic liquid functional groups and acrylate structural units was dissolved in dry dichloromethane, and 180 g of acryloyl chloride was added dropwise at room temperature. The reaction was carried out at room temperature for two hours, and the acryloyl-capped epoxy resin macromolecular material AIII was obtained by concentration.

[0137] 1 H NMR (500 MHz, Chloroform) δ 7.35–7.17 (m, 8H), 7.15–7.03 (m, 2H), 6.95–6.75 (m, 8H), 6.41 (dd, J=19.9, 4.5 Hz, 4H), 6.12 (dd, J=33.5, 19.8 Hz, 4H), 5.83 (dd, J=33.5, 4.4 Hz, 4H), 4.56–4.26 (m, 5H), 4.11 (ddd, J=10.6, 8.5, 5.1 Hz, 4H), 3.67–3.08 (m, 4H), 2.51–2.24 (m, 6H), 2.01–0.93 (m, 26H). 13 C NMR (125 MHz, Common NMR Solvents) δ 173.28, 164.38, 155.29, 141.42, 129.94, 128.27, 127.58, 116.41, 87.19, 75.03, 70.93, 70.04, 69.61, 61.01, 54.09, 48.17, 40.38, 37.52, 30.12, 27.60, 25.61, 24.40, 22.52.

[0138] The synthesis route is shown in Formula c:

[0139]

[0140] Example 4

[0141] Synthesis of epoxy resin-based polymer AIV:

[0142] 1.34 kg of bisphenol S epoxy resin (I-4-1) was dissolved in 2 L of dichloromethane. After adding 276 g of anhydrous potassium carbonate and stirring at room temperature for 1 hour, 788 g of the ionic liquid functional group compound with an alkyl chain (I-4-2) was added. After refluxing for 10 hours, it was cooled to room temperature, washed three times with water, dried over anhydrous sodium sulfate, and concentrated to remove the solvent, obtaining the epoxy resin intermediate compound I-4-3 containing an ionic liquid functional group.

[0143] 1 H NMR (500 MHz, Chloroform) δ 8.31–8.02 (m, 8H), 7.11–6.69 (m, 8H), 4.56–2.76 (m, 16H), 2.68–2.12 (m, 9H), 1.71–0.90 (m, 8H). 13 C NMR (125 MHz, Common NMR Solvents) δ 173.29, 162.29, 130.78, 129.50, 114.18, 75.03, 70.04, 69.61, 69.59, 61.01, 54.09, 51.46, 46.50, 40.38, 30.12, 27.64, 27.60, 26.58.

[0144] 1.96 kg of the intermediate compound (I-4-3) was dissolved in 2 L of anhydrous toluene. 360 g of glacial acetic acid was added to the reaction system, and it was refluxed for 24 hours, cooled, and concentrated to obtain the epoxy resin I-4-4 containing an ionic liquid functional group and an acrylate structural unit.

[0145] 1 H NMR (500 MHz, Chloroform) δ 8.26–7.95 (m, 8H), 7.06–6.65 (m, 8H), 6.46–5.66 (m, 8H), 4.70–3.91 (m, 9H), 3.79–2.21 (m, 12H), 1.73–1.04 (m, 6H). 13 C NMR (125 MHz, Common NMR Solvents) δ 173.28, 165.14, 162.29, 130.78, 129.94, 129.51, 128.27, 114.18, 89.84, 75.03, 72.30, 70.04, 69.61, 61.02, 54.10, 40.38, 30.13, 27.60, 24.40.

[0146] 1.08 g of epoxy resin I-4-4 containing ionic liquid functional groups and acrylate structural units was dissolved in dry dichloromethane. 180 g of acryloyl chloride was added dropwise at room temperature, and the reaction was carried out at room temperature for two hours. After concentration, an acryloyl-capped epoxy resin macromolecular material was obtained.

[0147] 1 H NMR(500MHz,Chloroform)δ8.18(d,J=7.5Hz,1H),7.12–6.99(m,1H),6.94(d,J=7.5Hz,1H),6.41(dd,J=10.0,2.1Hz,1H),6.12(dd,J=16.8,10.0Hz,1H),5.83(dd,J=16.8,2.1Hz,1H),4.46(dd,J=3.1,1.9Hz,1H),4.40–4.29(m,1H),4.15–2.33(m,2H),1.64–1.20(m,1H). 13 C NMR(125MHz,Common NMR Solvents)δ173.28,164.38,162.29,130.78,129.94,129.51,128.27,114.18,87.19,75.03,70.93,70.04,69.61,61.02,54.10,40.38,30.13,27.60,24.40.

[0148] The synthesis route is shown in formula d:

[0149]

[0150] Example 5

[0151] Synthesis of polyurethane-based polymer BI:

[0152] 2.51 kg of 3,5-diisocyanato-1-benzyl bromide (II-1-1) and 62 g of ethylene glycol (II-1-2) were dissolved in 5 L of anhydrous acetonitrile, and the reaction was refluxed for 5 hours. 251 g of 3,5-diisocyanato-1-benzyl bromide (II-1-1) was added, and the reaction was continued for 1 hour. The solvent was removed by reduced pressure concentration to obtain a polyurethane macromolecular material II-1-3.

[0153] 1 H NMR(500MHz,Chloroform)δ7.84(s,2H),7.74(s,1H),7.68(s,2H),7.63(s,2H),7.17(s,2H),7.13(s,2H),6.84(s,2H),4.77(d,J=25.5Hz,6H),4.31(s,8H).13 C NMR (125 MHz, Common NMR Solvents) δ 154.83, 145.09, 140.47, 134.83, 134.25, 134.10, 128.73, 120.60, 114.71, 112.74, 110.98, 105.34, 60.78, 31.04.

[0154] 1.75 kg of polyurethane macromolecular material I-1-3 was dissolved in anhydrous acetonitrile, and 380 g of alcohol compound (II-1-4) with acrylate was added dropwise at room temperature. After the addition was complete, the mixture was heated to reflux for 5 hours to obtain a polymer with a polymerizable acrylate structure (II-1-5) at the end.

[0155] 1 H NMR (500 MHz, Chloroform) δ 7.74 (t, J = 2.9 Hz, 3H), 7.68 (d, J = 3.1 Hz, 6H), 7.23 (s, 6H), 6.58–5.63 (m, 6H), 4.93 (s, 6H), 4.60–4.06 (m, 16H). 13 C NMR (125 MHz, Common NMR Solvents) δ 168.90, 154.83, 140.47, 134.10, 129.54, 127.80, 112.74, 110.98, 62.29, 60.78, 31.04.

[0156] 1.11 kg of the polymer with a polymerizable acrylate structure (II-1-5) at the end and 319 g of ionic liquid compound (II-1-6) were dissolved in 2 L of dichloromethane. 138 g of potassium carbonate was added, and the mixture was refluxed for 24 hours. After cooling, the solvent was removed by concentration under reduced pressure to obtain polyurethane-based polymer BI through an ionic liquid functionalization reaction.

[0157] 11H NMR (500 MHz, Chloroform) δ 7.74 (t, J = 1.4 Hz, 3H), 7.68 (d, J = 1.4 Hz, 6H), 7.29 (s, 4H), 7.19 (s, 2H), 6.41 (dd, J = 10.0, 2.1 Hz, 2H), 6.12 (dd, J = 16.8, 10.0 Hz, 2H), 5.83 (dd, J = 16.8, 2.1 Hz, 2H), 4.80 (s, 6H), 4.42–4.35 (m, 4H), 4.35–4.26 (m, 12H), 3.42 (t, J = 7.6 Hz, 3H), 3.38–3.30 (m, 12H), 3.24 (t, J = 5.3 Hz, 3H), 2.97 (t, J = 7.5 Hz, 3H), 2.90 (t, J = 5.3 Hz, 3H), 2.70 (t, J = 7.5 Hz, 3H), 2.42 (s, 9H), 1.60–1.45 (m, 12H), 1.33 (tt, J = 7.8, 5.4 Hz, 6H). 13 13C NMR (125 MHz, Common NMR Solvents) δ 168.90, 154.83, 149.81, 139.58, 134.73, 129.54, 127.80, 120.77, 119.58, 74.30, 71.61, 62.29, 60.78, 55.39, 50.40, 49.59, 41.00, 29.72, 27.49, 24.40.

[0158] The synthesis route is as shown in Formula e:

[0159]

[0160] Example 6

[0161] Synthesis of polyurethane-based polymer BII:

[0162] 2.51 kg of 3,5-diisocyanato-1-benzyl bromide (II-2-1) and 62 g of ethylene glycol (II-2-2) were dissolved in 5 L of anhydrous acetonitrile, and the mixture was refluxed for 5 hours. Then, 251 g of 3,5-diisocyanato-1-benzyl bromide (II-2-1) was added, and the reaction was continued for 1 hour. The solvent was removed by concentration under reduced pressure to obtain the polyurethane macromolecular material II-2-3.

[0163] 1.75 kg of the polyurethane macromolecular material I-1-3 was dissolved in anhydrous acetonitrile, and 380 g of p-hydroxybenzyl acrylate compound (II-2-4) was added dropwise at room temperature. After the addition was complete, the mixture was heated to reflux for 5 hours to obtain a polymer with a polymerizable acrylate structure at the end (II-2-5).

[0164] 1 1H NMR (500 MHz, Chloroform) δ 7.73 (t, J = 3.0 Hz, 3H), 7.67 (d, J = 2.9 Hz, 6H), 7.51 (s, 2H), 7.36 (s, 2H), 7.24 (s, 2H), 7.17 (s, 8H), 6.17 (ddd, J = 52.9, 26.6, 12.5 Hz, 4H), 5.73 (dd, J = 33.2, 4.8 Hz, 2H), 5.02 (s, 4H), 4.91 (s, 2H), 4.31 (s, 8H). 13 13C NMR (125 MHz, Common NMR Solvents) δ 165.45, 154.83, 154.46, 148.91, 147.20, 140.47, 134.11, 129.19, 127.17, 122.89, 122.67, 112.74, 110.98, 60.77, 31.04.

[0165] 1.28 kg of the polymer with a polymerizable acrylate structure (II-2-5) at the end and 319 g of the ionic liquid compound (II-2-6) were dissolved in 2 L of dichloromethane. 138 g of potassium carbonate was added, and the mixture was refluxed for 24 hours. After cooling, the solvent was removed by concentration under reduced pressure to obtain the polyurethane-based polymer BII through an ionic liquid functionalization reaction.

[0166] 1 1H NMR (500 MHz, Chloroform) δ 7.74 (t, J = 1.4 Hz, 3H), 7.68 (d, J = 1.4 Hz, 6H), 7.45 (s, 2H), 7.24 (s, 4H), 7.18 (s, 8H), 6.24 (dd, J = 10.1, 2.2 Hz, 2H), 6.10 (dd, J = 16.8, 10.0 Hz, 2H), 5.74 (dd, J = 16.8, 2.1 Hz, 2H), 4.80 (s, 6H), 4.31 (s, 8H), 3.54–2.26 (m, 37H), 1.76–1.13 (m, 18H).

[0167] 13 13C NMR (125 MHz, Common NMR Solvents) δ 165.45, 154.83, 154.46, 149.81, 148.91, 147.20, 139.58, 134.73, 129.19, 127.17, 122.89, 122.67, 120.77, 119.58, 74.30, 71.61, 60.78, 55.39, 50.40, 49.59, 41.00, 29.72, 27.49, 24.40.

[0168] The synthesis route is as shown in formula f:

[0169]

[0170] Example 7

[0171] Synthesis of water-soluble photoinitiator CI:

[0172] 2.34 kg of bis-(4-hydroxyphenyl)phosphine oxide (III-1-1) was dissolved in 5 L of dichloromethane, and 2.67 kg of acryloyl chloride was added dropwise at room temperature. After the addition was completed, the reaction was continued for 2 hours, and the solvent was removed by concentration to obtain the key intermediate III-1-2 capped with acrylate.

[0173] 1 H NMR(500MHz,Chloroform)δ7.75–7.68(m,4H),7.46–7.40(m,4H),6.24(dd,J=19.9,4.9Hz,2H),6.10(dd,J=33.1,19.9Hz,2H),5.74(dd,J=33.1,4.9Hz,2H). 13 C NMR(125MHz,Common NMR Solvents)δ165.45,149.40,149.37,132.04,131.94,129.19,127.17,124.97,123.95,123.91,123.88.

[0174] 684 g of the key intermediate III-1-2 capped with acrylate and 880 g of anhydride I-1-3 were dissolved in 2 L of toluene, and the reaction was refluxed for 6 hours. The solvent was removed by concentration under reduced pressure to obtain the compound III-1-4 containing the basic nucleus of TPO.

[0175] 1 H NMR(500MHz,Chloroform)δ7.37–7.27(m,6H),7.27–7.09(m,4H),6.17(ddd,J=52.9,26.5,12.4Hz,4H),5.74(dd,J=33.1,4.9Hz,2H),2.22(s,6H). 13 C NMR(125MHz,Common NMR Solvents)δ193.40,165.45,146.02,139.92,137.66,135.44,134.14,129.19,127.17,125.04,124.97,118.69,20.75.

[0176] 552 g of compound III-1-4 containing the TPO basic nucleus and 498 g of ionic liquid compound (III-1-5) were dissolved in 2 L of dichloromethane. 138 g of potassium carbonate was added, and the mixture was refluxed for 24 hours. After cooling, the solvent was removed by concentration under reduced pressure to obtain the target water-soluble polymerizable photoinitiator CI through an ionic liquid functionalization reaction.

[0177] 1 H NMR (500 MHz, Chloroform) δ 7.36–7.27 (m, 4H), 7.26–7.15 (m, 4H), 6.86 (s, 2H), 6.24 (dd, J = 19.9, 4.9 Hz, 2H), 6.10 (dd, J = 33.1, 19.9 Hz, 2H), 5.74 (dd, J = 33.1, 4.9 Hz, 2H), 4.11 (t, J = 10.2 Hz, 2H), 3.73 (s, 1H), 3.53 (s, 1H), 3.11 (s, 1H), 2.50–2.38 (m, 5H), 2.22 (s, 6H), 1.80 (p, J = 10.4 Hz, 2H), 1.54–1.19 (m, 6H). 13 C NMR (125 MHz, Common NMR Solvents) δ 193.40, 173.29, 165.45, 160.22, 146.02, 138.49, 135.44, 129.19, 128.60, 127.17, 124.97, 118.69, 116.01, 69.66, 61.01, 54.09, 40.38, 28.80, 27.64, 27.60, 26.58, 20.75.

[0178] The synthesis route is as shown in formula g:

[0179]

[0180] Example 8

[0181] Synthesis of water-soluble photoinitiator CII:

[0182] 2.34 kg of bis-(4-hydroxyphenyl) phosphine oxide (III-1-1) was dissolved in 5 L of dichloromethane. 3.12 kg of methacryloyl chloride was added dropwise at room temperature. After the addition was complete, the reaction was continued for 2 hours. The solvent was removed by concentration to obtain the key intermediate III-2-2 capped with methacrylate.

[0183] 11H NMR (500 MHz, Chloroform) δ 7.72 (d, J = 15.0 Hz, 4H), 7.43 (d, J = 15.0 Hz, 4H), 6.43 (dq, J = 4.0, 2.0 Hz, 2H), 6.18 (dq, J = 4.0, 2.0 Hz, 2H), 2.01 (t, J = 2.0 Hz, 6H). 13 13C NMR (125 MHz, Common NMR Solvents) δ 166.30, 150.29, 150.26, 133.90, 132.36, 132.26, 126.64, 124.97, 123.91, 123.77, 123.70, 19.10.

[0184] 740 g of the key intermediate III-1-2 capped with methacrylate and 880 g of the anhydride I-1-3 were dissolved in 2 L of toluene and refluxed for 6 hours. The solvent was removed by concentration under reduced pressure to obtain the compound III-2-4 containing the basic nucleus of TPO.

[0185] 1 1H NMR (500 MHz, Chloroform) δ 7.36–7.27 (m, 6H), 7.25–7.16 (m, 4H), 6.43 (dq, J = 4.0, 2.0 Hz, 2H), 6.18 (dq, J = 4.0, 2.0 Hz, 2H), 2.22 (s, 6H), 2.01 (t, J = 2.0 Hz, 6H). 13 13C NMR (125 MHz, Common NMR Solvents) δ 166.30, 156.14, 142.83, 138.74, 133.90, 132.31, 130.63, 129.23, 126.64, 126.12, 117.89, 20.75, 19.10.

[0186] 581 g of the compound III-1-4 containing the basic nucleus of TPO and 498 g of the ionic liquid compound (III-1-5) were dissolved in 2 L of dichloromethane. 138 g of potassium carbonate was added and the mixture was refluxed for 24 hours. After cooling, the solvent was removed by concentration under reduced pressure to obtain the target water-soluble polymerizable photoinitiator CII through an ionic liquid functionalization reaction.

[0187] 11H NMR (500 MHz, Chloroform) δ 7.34–7.31 (m, 1H), 7.31–7.28 (m, 2H), 7.24–7.21 (m, 3H), 7.20–7.18 (m, 1H), 6.86 (s, 2H), 6.43 (dq, J = 4.0, 2.0 Hz, 2H), 6.18 (dq, J = 4.0, 2.0 Hz, 2H), 4.88 (s, 2H), 4.44 (s, 2H), 4.11 (t, J = 10.1 Hz, 2H), 3.26 (t, J = 11.3 Hz, 1H), 3.05–2.90 (m, 4H), 2.22 (s, 6H), 2.01 (s, 6H), 1.80 (ttd, J = 15.7, 10.0, 1.3 Hz, 2H), 1.56–1.39 (m, 4H), 1.37–1.20 (m, 2H). 13 13C NMR (125 MHz, Common NMR Solvents) δ 204.77, 166.30, 161.59, 153.82, 139.97, 136.97, 133.90, 128.91, 127.10, 126.65, 125.16, 124.36, 118.12, 114.70, 81.84, 73.24, 69.66, 51.17, 37.81, 28.80, 27.64, 27.49, 26.58, 20.75, 19.10.

[0188] The synthesis route is as shown in Formula h.

[0189]

[0190] Example 9

[0191] The formula of the waterborne LED photocurable primer coating is shown in Tables 1 to 8.

[0192] Table 1 Formula 1 of the waterborne LED photocurable primer coating

[0193]

[0194] Table 2 Formula 2 of the waterborne LED photocurable primer coating

[0195]

[0196] Table 3 Formula 3 of the waterborne LED photocurable primer coating

[0197]

[0198] Table 4 Formula 4 of the waterborne LED photocurable primer coating

[0199]

[0200] Table 5 Formulation 5 of Waterborne LED UV-Curable Primer Coating

[0201]

[0202] Table 6 Formulation 6 of Waterborne LED UV-Curable Primer Coating

[0203]

[0204]

[0205] Table 7 Formulation 7 of Waterborne LED UV-Curable Primer Coating

[0206]

[0207] Table 8 Formulation 8 of Waterborne LED UV-Curable Primer Coating

[0208]

[0209] Example 9

[0210] The formulations of the waterborne LED UV-curable topcoat are shown in Tables 9 to 12.

[0211] Table 9 Formulation 1 of Waterborne LED UV-Curable Topcoat

[0212]

[0213] Table 10 Formulation 2 of Waterborne LED UV-Curable Topcoat

[0214]

[0215] Table 11 Formulation 3 of Waterborne LED UV-Curable Topcoat

[0216]

[0217] Table 12 Formulation 4 of Waterborne LED UV-Curable Topcoat

[0218]

[0219] Example 10

[0220] The primers and topcoats are used with the formulations involved in the foregoing examples, and the combination schemes are shown in Table 13.

[0221] Table 13 Combined Formulation of Primer and Topcoat

[0222]

[0223] The painting process is as Figure 1As shown

[0224] Among them, the specific painting process of Scheme 1 is as follows:

[0225] Clean the surface of the substrate with zirconium salt and deionized water to remove oil and rust on the surface of the metal substrate, and then dry it. Spray the surface of the substrate with Primer Formula 1, irradiate it with UV-LED for 10 minutes to crosslink and cure it, and then further dry it with medium-wave infrared and long-wave infrared respectively. Spray with Topcoat Formula 1 as the topcoat, irradiate it with UV-LED for 10 minutes to crosslink and cure it, and then further dry it with medium-wave infrared and long-wave infrared respectively, and then it can be shipped. Treat a small amount of VOC tail gas, and there is no waste water and waste gas emission throughout the process.

[0226] The painting methods of Schemes 2 to 32 are the same as that of Scheme 1.

[0227] Test the hardness, adhesion, solvent resistance (number of alcohol scrubbing times) and VOC release amount of the coatings obtained from Schemes 1 to 32. The hardness of the cured film is carried out in accordance with GB / T 6739—1996 "Pencil Method for Measuring Film Hardness", and the test range is 4B to 6H; the adhesion test is carried out in accordance with the national standard GB / T 9286—1998; the yellowing resistance test is carried out in accordance with GB-T 9761-2008 "Visual Colorimetry of Paints and Varnishes - Paints"; the solvent resistance test is carried out in accordance with Method A (immersion method) in GB 9274—1988 "Determination of Resistance of Paints and Varnishes to Liquid Media"; and the VOC release amount test is carried out in accordance with GB / T23986—2009 "Determination of Volatile Organic Compounds (VOC) Content in Paints and Varnishes - Gas Chromatography Method".

[0228] The obtained results are shown in Table 14.

[0229] Table 14 Performance Test Results of Coatings Obtained from Schemes 1 to 32

[0230]

[0231]

[0232] The waterborne LED photocurable coating prepared by using the epoxy resin-based polymer, polyurethane-based polymer and water-soluble photoinitiator of the present invention as raw materials has good hardness, adhesion and solvent resistance, and its VOC release amount is 70 - 110 mg / mL.

[0233] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A water-soluble photoinitiator having the structure shown in Formula C: In formula C, R is independently C y H 2y+1 , and y is from 0 to 20; m is from 0 to 5.

2. The water-soluble photoinitiator according to claim 1, wherein Having the structure shown in Formula CI or CII:

3. A method for preparing the water-soluble photoinitiator according to claim 1, comprising the following steps: A compound having the structure shown in Formula C-1 reacts with a compound having the structure shown in Formula C-2 by a substitution reaction to obtain a compound having the structure shown in Formula C-3; A compound having the structure shown in Formula C-3 reacts with a compound having the structure shown in Formula C-4 by a substitution reaction to obtain a compound having the structure shown in Formula C-5; A compound having the structure shown in Formula C-5 reacts with an ionic liquid having the structure shown in Formula C-6 by a substitution reaction to obtain a photocatalyst having the structure shown in Formula C; 4. Use of the water-soluble photoinitiator according to claim 1 or 2 or the water-soluble photoinitiator prepared by the preparation method according to claim 3 as a photoinitiator for waterborne LED photocurable coatings.

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