A polymerizable aqueous photoinitiator, its preparation method and application

Abstract

The application provides a polymerizable aqueous photoinitiator and a preparation method and application thereof, and belongs to the technical field of initiators.The application solves the problems that current commercialized photoinitiators are easy to migrate and pollute products, are easy to volatilize and pollute the environment, and are harmful to human health, and develops a new type of polymerizable aqueous photoinitiator, which is environment-friendly and cannot migrate in coating products, and the principle is as follows: a carbazole containing a quaternary ammonium salt is combined with an oxime ester compound, the activity of the oxime ester is retained, and the quaternary ammonium salt structure can be well dispersed in an aqueous solution; a triphenylamine structure containing an acrylic ester structural unit is introduced into the structural formula, the excitation wavelength of the initiator is regulated, and the initiator can self-generate polymerization; the photoinitiator provided by the application can be well dispersed in an aqueous solution, can self-generate photopolymerization, and cannot migrate in coating products.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of initiators, in particular to a polymerizable aqueous photoinitiator and a preparation method and application thereof. BACKGROUND

[0002] Polymer materials have penetrated into all aspects of human life, and polymer materials, also known as polymer materials, are macromolecular compounds formed by a large number of small molecular compounds through chemical bonds. The common polymer materials in daily production and life mainly include synthetic rubber, synthetic fiber, synthetic plastic and the like. These polymer materials have been widely used in daily life, such as clothing industry, daily necessities and various industrial materials, to meet the demand of various industries for polymer materials. In addition, polymer materials can be used for nanometer polymer material composite application, biodegradable polymer material, polymer material functionalization and aerospace field. In the polymer products in daily life, most of them are artificially synthesized, using polymerizable small molecules as precursors and adding appropriate initiators to form polymer materials. In this process, the residues of chemical raw materials and solvents have adverse effects on human beings and the environment. For example, coatings, electronic products, ink printing, food packaging and the like are necessities in people's daily life, and if there are residues or migration of chemical harmful substances, it will seriously endanger human health and regional ecological environment safety.

[0003] Photocuring (photopolymerization) technology as a new type of surface treatment technology of materials refers to a process that monomers or oligomers can be polymerized and crosslinked under the action of visible light / ultraviolet light irradiation to realize curing. The photocuring system mainly consists of four parts of photoactive monomer, photoactive oligomer, photoinitiator and additive. When the photocuring system is irradiated with light, the photoinitiator in the system is excited and decomposed to generate active free radicals, which collide with double bonds in the system and react to form growing chains. This reaction continues to extend, so that the double bonds in the photoactive monomer and oligomer are opened, and the photocured product is formed by crosslinking. Therefore, the photoinitiator plays an important role in photocuring.

[0004] The traditional photoinitiator is a small molecule photoinitiator, which has the problems of easy migration to contaminate products, easy volatilization to pollute the environment and harmful substance residues to endanger human health. SUMMARY

[0005] Therefore, the purpose of the present application is to provide a polymerizable aqueous photoinitiator and a preparation method and application thereof. The polymerizable aqueous photoinitiator provided by the present application has high adhesion to glass.

[0006] In order to achieve the above-mentioned purpose of the application, the present application provides the following technical solutions.

[0007] The present application provides a polymerizable aqueous photoinitiator, which has a structure shown in formula Y:

[0008]

[0009] R in formula Y is an alkyl chain C x H 2x+1 wherein x is an integer from 0 to 20;

[0010] n is an integer from 0 to 20;

[0011] R1, R2 and R3 are independently benzyl, substituted benzyl, alkyl, halogen-substituted alkyl or halogen-substituted aryl;

[0012] X - is fluoride, chloride, bromide, iodide, hexafluorophosphate or nitrate.

[0013] Preferably, the polymerizable aqueous photoinitiator has a structure as shown in any one of Y1 to Y12:

[0014]

[0015]

[0016] The present application also provides a preparation method of the polymerizable aqueous photoinitiator described in the technical solution above, comprising the following steps:

[0017] mixing carbazole-1-formaldehyde, hydroxylamine hydrochloride, sodium acetate and a solvent to perform a nucleophilic addition reaction to obtain a carbazole formaldehyde oxime;

[0018] mixing the carbazole formaldehyde oxime, benzothiophene carboxylic acid, dicyclohexyl carbodiimide and an organic solvent to perform a dehydration reaction to obtain an intermediate compound;

[0019] mixing the intermediate compound, a terminal dibromo-substituted alkane and an organic solvent to perform a first substitution reaction to obtain a first substitution product;

[0020] mixing the first substitution product, anhydrous aluminum chloride, p-nitrobenzoyl chloride and an organic solvent to perform a Friedel-Crafts acylation reaction to obtain a Friedel-Crafts acylation product;

[0021] mixing the Friedel-Crafts acylation product, iron powder, an aqueous ammonium chloride solution and an organic solvent to perform a reduction reaction to obtain a reduction product;

[0022] mixing p-bromophenol, acryloyl chloride and an organic solvent to perform a second substitution reaction to obtain a second substitution product;

[0023] mixing the reduction product, the second substitution product, anhydrous cesium carbonate and an organic solvent to perform a third substitution reaction to obtain a third substitution product;

[0024] Mixing the third substitution product with an amine substance to perform a nucleophilic substitution reaction to obtain a nucleophilic substitution product;

[0025] Mixing the nucleophilic substitution product with a sodium salt to perform ion exchange to obtain the polymerizable aqueous photoinitiator.

[0026] Preferably, the molar ratio of the carbazole-1-formaldehyde to hydroxylamine hydrochloride is 1:2.

[0027] Preferably, the molar ratio of the intermediate compound to the terminal dibromine-substituted alkane is 4:5.

[0028] Preferably, the molar ratio of the first substitution product to p-nitrobenzoyl chloride is 3:5.

[0029] Preferably, the molar ratio of the p-bromophenol to acryloyl chloride is 1:1.2.

[0030] Preferably, the molar ratio of the third substitution product to the amine substance is 1:2.

[0031] Preferably, the temperature of the reduction reaction is 80-90 DEG C, and the time is 10-24 h.

[0032] The application further provides application of the polymerizable aqueous photoinitiator in photocuring coating.

[0033] The application provides a polymerizable aqueous photoinitiator, which has a structure shown in formula Y. DETAILED DESCRIPTION

[0034] The application provides a polymerizable aqueous photoinitiator, which has a structure shown in formula Y.

[0035]

[0036] In formula Y, R is an alkyl chain C x H 2x+1 wherein x is an integer of 0-20.

[0037] n is an integer of 0-20.

[0038] R1, R2 and R3 are independently benzyl, substituted benzyl, alkyl, halogen- substituted alkyl or halogen-substituted aryl;

[0039] X - is fluoride, chloride, bromide, iodide, hexafluorophosphate or nitrate.

[0040] In the present application, the polymerizable aqueous photoinitiator preferably has any of the structures shown in Y1-12:

[0041]

[0042]

[0043] The present application also provides a preparation method of the polymerizable aqueous photoinitiator described in the above technical solution, comprising the following steps:

[0044] Carbazole-1-formaldehyde, hydroxylamine hydrochloride, sodium acetate and a solvent are mixed to perform a nucleophilic addition reaction to obtain a carbazole formaldehyde oxime;

[0045] The carbazole formaldehyde oxime, benzothiophene carboxylic acid, dicyclohexyl carbodiimide and an organic solvent are mixed to perform a dehydration reaction to obtain an intermediate compound;

[0046] The intermediate compound, a terminal dibromo-substituted alkane and an organic solvent are mixed to perform a first substitution reaction to obtain a first substitution product;

[0047] The first substitution product, anhydrous aluminum chloride, p-nitrobenzoyl chloride and an organic solvent are mixed to perform a Friedel-Crafts acylation reaction to obtain a Friedel-Crafts acylation product;

[0048] The Friedel-Crafts acylation product, iron powder, an aqueous ammonium chloride solution and an organic solvent are mixed to perform a reduction reaction to obtain a reduction product;

[0049] P-bromophenol, acryloyl chloride and an organic solvent are mixed to perform a second substitution reaction to obtain a second substitution product;

[0050] The reduction product, the second substitution product, anhydrous cesium carbonate and an organic solvent are mixed to perform a third substitution reaction to obtain a third substitution product;

[0051] The third substitution product and an amine substance are mixed to perform a nucleophilic substitution reaction to obtain a nucleophilic substitution product;

[0052] The nucleophilic substitution product and a sodium salt are mixed to perform ion exchange to obtain the polymerizable aqueous photoinitiator.

[0053] In the present application, if not specifically stated, the raw materials used are commercially available in the art.

[0054] In the present application, the principle of the preparation method is shown in the following formula:

[0055]

[0056] The present application carries out nucleophilic addition reaction by mixing carbazole-1-formaldehyde, hydroxylamine hydrochloride, sodium acetate and solvent to obtain carbazole formaldehyde oxime.

[0057] In the present application, the molar ratio of carbazole-1-formaldehyde to hydroxylamine hydrochloride is preferably 1:2.

[0058] In the present application, the molar ratio of carbazole-1-formaldehyde to sodium acetate is preferably 1:3.

[0059] In the present application, the solvent is preferably ethanol-water mixture, and the volume ratio of ethanol to water in the ethanol-water mixture is preferably 3:7.

[0060] In the present application, the dosage ratio of carbazole-1-formaldehyde to solvent is preferably 1 mol:1000 mL.

[0061] In the present application, the temperature of the nucleophilic addition reaction is preferably 95℃, and the time is preferably 12h.

[0062] In the specific embodiment of the present application, the ethanol and H2O are configured as solvent, the carbazole formaldehyde (A) is added to the solvent, the hydroxylamine hydrochloride (B) and sodium acetate are sequentially added under constant stirring, heated to 95℃, stirred for 12h, the reaction is detected by thin layer chromatography, after the raw material carbazole formaldehyde (A) is completely reacted, cooled to room temperature, ethyl acetate is added to the reaction solution for extraction for 3 times, the combined organic phase is distilled under reduced pressure to remove the organic solvent, a solid is obtained, then the solid is recrystallized by using a mixed solvent of dichloromethane and petroleum ether to obtain the carbazole formaldehyde oxime (C).

[0063] After obtaining the carbazole formaldehyde oxime, the present application carries out dehydration reaction by mixing the carbazole formaldehyde oxime, benzothiophene carboxylic acid, dicyclohexyl carbodiimide and organic solvent to obtain an intermediate compound.

[0064] In the present application, the molar ratio of carbazole formaldehyde oxime to benzothiophene carboxylic acid is preferably 1:1.

[0065] In the present application, the molar ratio of carbazole formaldehyde oxime to dicyclohexyl carbodiimide is preferably 1:1.1.

[0066] In the present application, the organic solvent is preferably dichloromethane.

[0067] In the present application, the dosage ratio of carbazole formaldehyde oxime to organic solvent is preferably 0.5 mol:1000 mL.

[0068] In the embodiment of the present application, the intermediate compound (E) is obtained by adding the benzothiophene carboxylic acid (D), dicyclohexyl carbodiimide (DCC), carbazole formaldehyde oxime (C) and dichloromethane first, stirring at room temperature overnight, purifying by column chromatography (V (petroleum ether): V (ethyl acetate) = 4:1) after the reaction is completed, and drying.

[0069] After obtaining the intermediate compound, the present application mixes the intermediate compound, the terminal dibromosubstituted alkane and the organic solvent to perform a first substitution reaction to obtain a first substitution product.

[0070] In the present application, the molar ratio of the intermediate compound to the terminal dibromosubstituted alkane is preferably 4:5.

[0071] In the present application, the organic solvent is preferably dichloromethane.

[0072] In the present application, the usage ratio of the intermediate compound to the organic solvent is preferably 0.4 mol: 1000 mL.

[0073] In the present application, the first substitution reaction is preferably performed in an alkaline environment, the alkaline environment is preferably provided by potassium carbonate, and the molar ratio of the intermediate compound to potassium carbonate is preferably 4:10.

[0074] In the embodiment of the present application, the intermediate compound (E), potassium carbonate, the terminal dibromosubstituted alkane (F) and dichloromethane are mixed, stirred at room temperature for 24 hours, the reaction is detected to be complete by thin layer chromatography, filtered, the filter residue is removed, the organic phase is washed with pure water three times, dried and concentrated to obtain the first substitution product (G).

[0075] After obtaining the first substitution product, the present application mixes the first substitution product, anhydrous aluminum chloride, p-nitrobenzoyl chloride and an organic solvent to perform a Friedel-Crafts acylation reaction to obtain a Friedel-Crafts acylation product.

[0076] In the present application, the molar ratio of the first substitution product to p-nitrobenzoyl chloride is preferably 3:5.

[0077] In the present application, the molar ratio of the first substitution product to anhydrous aluminum chloride is preferably 3:10.

[0078] In the present application, the organic solvent is preferably dichloromethane.

[0079] In the present application, the usage ratio of the first substitution product to the organic solvent is preferably 0.3 mol: 1000 mL.

[0080] In the embodiment of the present application, the first substitution product (G) is preferably dissolved in dichloromethane, anhydrous aluminum chloride is added at 0°C, after addition, stirring at room temperature for 2h, p-nitrobenzoyl chloride (H) is added, stirring at room temperature overnight, the reaction is quenched with saturated aqueous ammonium chloride solution, washed with water three times, dried and concentrated to obtain the Friedel-Crafts acylation product, which is preferably directly used in the next step without purification.

[0081] After obtaining the Friedel-Crafts acylation product, the present application mixes the Friedel-Crafts acylation product, iron powder, aqueous ammonium chloride solution and organic solvent to carry out a reduction reaction to obtain a reduction product.

[0082] In the present application, the temperature of the reduction reaction is preferably 80-90°C, and the time is preferably 10-24h.

[0083] In the embodiment of the present application, the Friedel-Crafts acylation product is preferably dissolved in toluene, iron powder and 1mol / L aqueous ammonium chloride solution are added, stirring at 80°C for 10h, cooling to room temperature, washing with water three times, concentrating and drying, recrystallizing with dichloromethane and petroleum ether to obtain the reduction product (J).

[0084] The present application mixes p-bromophenol, acryloyl chloride and an organic solvent to carry out a second substitution reaction to obtain a second substitution product.

[0085] In the present application, the molar ratio of p-bromophenol to acryloyl chloride is preferably 1:1.2.

[0086] In the present application, the organic solvent is preferably dichloromethane.

[0087] In the present application, the ratio of the amount of p-bromophenol to the organic solvent is preferably 1mol:1000mL.

[0088] In the embodiment of the present application, the p-bromophenol (K) is preferably dissolved in dichloromethane, acryloyl chloride (L) is added dropwise at room temperature, after dropwise addition, stirring at room temperature for 4h, the reaction is quenched with ice water, washed with saturated aqueous sodium bicarbonate solution three times, dried and concentrated to obtain the second substitution product (M).

[0089] After obtaining the second substitution product and the reduction product, the present application mixes the reduction product, the second substitution product, anhydrous cesium carbonate and an organic solvent to carry out a third substitution reaction to obtain a third substitution product.

[0090] In the present application, the molar ratio of the reduction product to the second substitution product is preferably 1:3.

[0091] In the present application, the molar ratio of the reduction product to anhydrous cesium carbonate is preferably 1:3.

[0092] In the present application, the organic solvent is preferably dimethyl sulfoxide.

[0093] In the present application, the use amount ratio of the reduction product to the organic solvent is preferably 0.1 mol:500 mL.

[0094] In the present application, the temperature of the third substitution reaction is preferably 140℃, and the time is preferably 12 h.

[0095] In a specific embodiment of the present application, the reduction product (J), the second substitution product (M) and anhydrous cesium carbonate are added into dimethyl sulfoxide, heated and stirred at 140℃ under nitrogen atmosphere for 12 h, cooled to room temperature, water is added, extracted with dichloromethane for 3 times, the dichloromethane layer is washed with water for 5 times, dried and concentrated, and column chromatography is performed with dichloromethane and petroleum ether to obtain the third substitution product (P).

[0096] After obtaining the third substitution product, the present application mixes the third substitution product with an amine substance to perform a nucleophilic substitution reaction to obtain a nucleophilic substitution product.

[0097] In the present application, the molar ratio of the third substitution product to the amine substance is preferably 1:2.

[0098] In the present application, the nucleophilic substitution reaction is preferably performed in a solvent, and the solvent is preferably an ethanol-water mixture, and the volume ratio of ethanol to water in the ethanol-water mixture is preferably 1:1.

[0099] In the present application, the use amount ratio of the third substitution product to the solvent is preferably 0.05 mol:500 mL.

[0100] In the present application, the temperature of the nucleophilic substitution reaction is preferably 90℃.

[0101] In a specific embodiment of the present application, the third substitution product (P) and the amine substance (Q) are dissolved in a solvent, and reacted at 90℃ overnight, and concentrated under reduced pressure to obtain a nucleophilic substitution product.

[0102] After obtaining the nucleophilic substitution product, the present application mixes the nucleophilic substitution product with a sodium salt to perform ion exchange to obtain the polymerizable aqueous photoinitiator Y.

[0103] In the present application, the ion exchange is preferably performed in an aqueous solution.

[0104] In the present application, the sodium salt is preferably sodium fluoride, sodium chloride, sodium iodide, sodium hexafluorophosphate or sodium nitrate.

[0105] The present application also provides an application of the polymerizable aqueous photoinitiator in the above technical solution in photocuring coatings.

[0106] The application is not particularly limited in the specific manner of the application, and a manner well known to those skilled in the art can be used.

[0107] The technical solutions in the application will be described clearly and completely below in combination with the embodiments in the application. Obviously, the described embodiments are only some of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the application.

[0108] The synthesis of the polymerizable aqueous photoinitiator Y-1 in Example 1 is as shown in the following formula:

[0109]

[0110] 300 mL of ethanol and 700 mL of H2O were configured into a mixed solvent, and 195 g (1 mol) of carbazole formaldehyde (1) was added into the solvent. Hydroxylamine hydrochloride (138 g, 2 mol) and sodium acetate (24.6 g, 3 mol) were sequentially added under constant stirring, heated to 95°C, and stirred for about 12 h. The reaction was detected by thin layer chromatography. After the raw material carbazole formaldehyde (1) was completely reacted, the reaction solution was cooled to room temperature, and 3 x 1 L of ethyl acetate was added for extraction three times. The combined organic phase was distilled under reduced pressure to remove the organic solvent, and a solid was obtained. Then, the solid was recrystallized using a mixed solvent of dichloromethane and petroleum ether to obtain 183 g of carbazole formaldehyde oxime (3). 1 H NMR (500 MHz, CDCl3) δ 8.23-8.14 (m, 1H), 8.07 (s, 1H), 8.00 (dd, J = 15.0, 2.9 Hz, 1H), 7.73 (d, J = 15.0 Hz, 1H), 7.67 (d, J = 2.9 Hz, 1H), 7.31 (s, 1H), 7.26-7.11 (m, 2H).

[0111] In a 2L single-mouth flask, benzothiophene carboxylic acid (4) (89 g, 0.5 mol), dicyclohexyl carbodiimide (DCC) (113 g, 0.55 mmol), carbazole formaldehyde oxime (3, 105 g, 0.5 mol) and 1 L of dichloromethane were added, and stirred at room temperature overnight. After the reaction was completed, it was purified by column chromatography (V(petroleum ether):V(ethyl acetate)=4:1), and dried to obtain 173 g of intermediate compound 5. 1HNMR (500 MHz, CDC13) δ 8.35 (d, J = 2.9 Hz, 1H), 8.30 (s, 1H), 8.23-8.11 (m, 1H), 8.00 (dd, J = 15.0, 2.9 Hz, 1H), 7.84-7.68 (m, 4H), 7.57 (s, 1H), 7.43-7.35 (m, 1H), 7.35-7.26 (m, 2H), 7.25-7.10 (m, 2H).

[0112] 148 g (0.4 mol) of compound 5, 138 g (1 mol) of potassium carbonate and 93 g (0.5 mol) of 1,2-dibromoethane (6) were mixed with 1 L of dichloromethane, stirred at room temperature for 24 h, and the reaction was confirmed to be complete by thin layer chromatography. The reaction mixture was filtered, the filtrate was washed with pure water three times, and the organic phase was dried and concentrated to obtain 163 g of the intermediate compound (7). 1 H NMR (500 MHz, CDC13) δ 8.36 (d, J = 3.1 Hz, 1H), 8.31 (s, 1H), 7.98 (ddd, J = 20.2, 15.0, 3.0 Hz, 2H), 7.84-7.69 (m, 4H), 7.64 (dd, J = 15.0, 3.2 Hz, 1H), 7.54 (td, J = 14.9, 3.0 Hz, 1H), 7.38-7.25 (m, 3H), 4.59 (td, J = 15.2, 5.8 Hz, 2H), 3.85 (t, J = 15.2 Hz, 2H).

[0113] 0.3 mol (142.8 g) of compound (7) was dissolved in 1 L of dichloromethane, and anhydrous aluminum chloride (1 mol, 133 g) was added at 0°C. After the addition, it was stirred at room temperature for 2 h, and p-nitrobenzoyl chloride (8) (0.5 mol, 92.5 g) was further added, and it was stirred at room temperature overnight. The reaction was quenched with saturated aqueous ammonium chloride solution, washed with water three times, dried, and concentrated. Without purification, it was directly used in the next reaction. The crude product (9) was dissolved in 1 L of toluene, and 50 g of iron powder, 10 mL of 1 mol / L aqueous ammonium chloride solution were added, and it was stirred at 80°C for 10 h. After being cooled to room temperature, it was washed with water three times, concentrated, and dried. 156.3 g of intermediate compound (10) was recrystallized from dichloromethane and petroleum ether.1H NMR (500 MHz, CDCl3) δ 8.36 (d, J = 2.9 Hz, 1H), 8.31 (s, 1H), 8.04-7.94 (m, 2H), 7.88-7.68 (m, 5H), 7.60-7.50 (m, 2H), 7.45 (dd, J = 15.0, 3.1 Hz, 1H), 7.37-7.26 (m, 2H), 6.45-6.24 (m, 2H), 4.62 (td, J = 15.1, 5.5 Hz, 2H), 3.88 (t, J = 15.2 Hz, 2H).

[0114] 171 g (1 mol) of p-bromophenol (11) was dissolved in 1 L of dichloromethane, and 108.0 g (1.2 mol) of acryloyl chloride (12) was added dropwise at room temperature. After the dropwise addition was completed, it was further stirred at room temperature for 4 h, and the reaction was quenched with ice water. It was washed with saturated aqueous sodium bicarbonate solution three times, dried, and concentrated to obtain 201 g of intermediate compound (13). 1 1H NMR (500 MHz, CDCl3) δ 7.55 (d, J = 7.5 Hz, 2H), 7.18 (d, J = 7.5 Hz, 2H), 6.24 (dd, J = 10.1, 2.2 Hz, 1H), 6.10 (dd, J = 16.8, 10.0 Hz, 1H), 5.74 (dd, J = 16.8, 2.1 Hz, 1H).

[0115] 59.5 g (0.1 mol) of intermediate compound (10) was reacted with 67.5 g (0.3 mol) of compound (13), 97.5 g (0.3 mol) of anhydrous cesium carbonate, and 500 mL of dimethyl sulfoxide under nitrogen at 140°C for 12 h. After being cooled to room temperature, 1 L of water was added, and it was extracted with dichloromethane three times. The dichloromethane layer was washed with water five times, dried, and concentrated. By column chromatography using dichloromethane and petroleum ether, 124.5 g of intermediate compound (14) was obtained. 1H NMR (500 MHz, CDC13) δ 8.36 (d, J = 3.0 Hz, 1H), 8.31 (s, 1H), 8.00 (dd, J = 15.0, 2.9 Hz, 1H), 7.91 (d, J = 2.9 Hz, 1H), 7.86 - 7.66 (m, 7H), 7.45 (dd, J = 15.0, 3.1 Hz, 1H), 7.37 - 7.24 (m, 4H), 7.20 - 7.11 (m, 4H), 7.10 - 7.00 (m, 4H), 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), 4.59 (t, J = 15.2 Hz, 2H), 3.89 (t, J = 15.1 Hz, 2H).

[0116] 44.4 g (0.05 mol) of compound (14) and 16.4 (0.1 mol) of methylbutylbenzylamine (15) were dissolved in 500 mL of ethanol-water (mass ratio 1:1) mixed solution, and reacted at 90°C overnight. After concentration under reduced pressure, 38.2 g of the target compound Y-1 was obtained. 1 H NMR (500 MHz, CDC13) δ 8.36 (d, J = 3.0 Hz, 1H), 8.31 (s, 1H), 8.00 (dd, J = 15.0, 2.9 Hz, 1H), 7.91 (d, J = 2.9 Hz, 1H), 7.86 - 7.66 (m, 7H), 7.45 (dd, J = 15.0, 3.1 Hz, 1H), 7.37 - 7.24 (m, 4H), 7.20 - 7.11 (m, 4H), 7.10 - 7.00 (m, 4H), 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), 4.59 (t, J = 15.2 Hz, 2H), 3.89 (t, J = 15.1 Hz, 2H).

[0117] Example 2 Synthesis of polymerizable aqueous photoinitiator Y-2, the principle is shown in the following formula:

[0118]

[0119] 171 g (1 mol) of p-bromophenol (2-1) was dissolved in 1 L of dichloromethane, and 124.8 g (1.2 mol) of methacryloyl chloride (2-2) was added dropwise at room temperature. After the dropwise addition was completed, stirring was continued at room temperature for 4 h, and the reaction was quenched by adding ice water. The quenched reaction mixture was washed with saturated aqueous sodium bicarbonate solution three times, and the concentrated 197 g of the intermediate compound (2-3) was dried. 1 H NMR (500 MHz, Chloroform) δ 7.69 - 7.38 (m, 2H), 7.27 - 7.04 (m, 2H), 6.43 (dq, J = 4.0, 2.0 Hz, 1H), 6.18 (dq, J = 4.0, 2.0 Hz, 1H), 2.01 (t, J = 2.0 Hz, 3H).

[0120] 59.5 g (0.1 mol) of the intermediate compound (10) was dissolved in 500 mL of dimethyl sulfoxide, and 72.3 g (0.3 mol) of the compound (2-3), 97.5 g (0.3 mol) of cesium carbonate, and 500 mL of dimethyl sulfoxide were added thereto. The mixture was heated and stirred at 140°C for 12 h under a nitrogen atmosphere, and then cooled to room temperature. 1 L of water was added to the reaction mixture, and the mixture was extracted with dichloromethane three times. The dichloromethane layer was washed with water five times, and then dried and concentrated. The concentrated mixture was column-chromatographed with dichloromethane and petroleum ether to obtain 118.2 g of the intermediate compound (2-4). 1 H NMR (500 MHz, Chloroform) δ 8.36 (d, J = 1.4 Hz, 1H), 8.31 (s, 1H), 8.00 (dd, J = 7.5, 1.4 Hz, 1H), 7.90 (d, J = 1.4 Hz, 1H), 7.84 (d, J = 1.4 Hz, 1H), 7.79 (dd, J = 5.4, 3.5 Hz, 2H), 7.76 - 7.66 (m, 4H), 7.45 (dd, J = 7.5, 1.4 Hz, 1H), 7.32 (dd, J = 5.5, 3.5 Hz, 2H), 7.28 (d, J = 7.5 Hz, 2H), 7.15 (d, J = 7.5 Hz, 4H), 7.06 (d, J = 7.5 Hz, 4H), 6.52 - 6.29 (m, 2H), 6.28 - 6.07 (m, 2H), 4.74 - 4.44 (m, 2H), 3.86 (t, J = 7.6 Hz, 2H), 2.01 (s, 6H).

[0121] 45.8 g (0.05 mol) of the compound (14) and 16.4 (0.1 mol) of methylbutylbenzylamine (15) were dissolved in 500 mL of a mixture of ethanol and water (1:1 by volume), and the mixture was reacted at 90°C overnight. The reaction mixture was concentrated under reduced pressure to obtain 41.8 g of the target compound Y-2. 1HNMR (500 MHz, Chloroform) δ 8.36 (d, J = 2.9 Hz, 1H), 8.31 (s, 1H), 8.09 (d, J = 2.9 Hz, 1H), 8.00 (dd, J = 15.0, 2.9 Hz, 1H), 7.85 - 7.66 (m, 7H), 7.45 (dd, J = 15.0, 3.1 Hz, 1H), 7.36 - 7.18 (m, 9H), 7.18 - 7.11 (m, 4H), 7.10 - 7.00 (m, 4H), 6.43 (dq, J = 4.0, 2.0 Hz, 2H), 6.18 (dq, J = 4.0, 2.0 Hz, 2H), 4.77 (s, 2H), 4.59 (t, J = 14.8 Hz, 2H), 3.69 (t, J = 14.8 Hz, 2H), 3.48 - 3.34 (m, 5H), 2.01 (t, J = 2.0 Hz, 6H), 1.88 (p, J = 15.4 Hz, 2H), 1.35 - 1.15 (m, 2H), 0.89 (dd, J = 13.4, 12.8 Hz, 3H).

[0122] Example 3 Synthesis of polymerizable aqueous photoinitiator Y-3, the principle is shown as follows:

[0123]

[0124] 171 g (1 mol) of p-bromophenol (3-1) was dissolved in 1 L of dichloromethane, 175.9 g (1.2 mol) of butyl acryloyl chloride was added dropwise at room temperature, after the addition was completed, it was continuously stirred at room temperature for 4 h, and then quenched with ice water, washed with saturated aqueous sodium bicarbonate solution for 3 times, and dried and concentrated to obtain 243.5 g of intermediate compound (3-3). 1 HNMR (500 MHz, Chloroform) δ 7.79 - 7.42 (m, 2H), 7.28 - 7.02 (m, 2H), 6.12 (dt, J = 4.1, 1.9 Hz, 1H), 5.37 (dt, J = 4.0, 1.9 Hz, 1H), 2.40 (ddd, J = 9.0, 8.5, 7.1 Hz, 2H), 1.54 - 1.13 (m, 4H), 0.93 (dd, J = 15.1, 10.3 Hz, 3H).

[0125] 59.5 g (0.1 mol) of intermediate compound (10) was reacted with 84.9 g (0.3 mol) of compound (3-3), 97.5 g (0.3 mol) of anhydrous cesium carbonate, and 500 mL of dimethyl sulfoxide under nitrogen environment, heated and stirred at 140°C for 12 h, cooled to room temperature, added 1 L of water, extracted with dichloromethane for 3 times, and washed with water for 5 times. After drying and concentration, column chromatography with dichloromethane and petroleum ether was performed to obtain 136.5 g of intermediate compound (3-4).1 H NMR (500 MHz, Chloroform) δ 8.36 (d, J = 3.1 Hz, 1H), 8.31 (s, 1H), 8.00 (dd, J = 15.0, 2.9 Hz, 1H), 7.95 (d, J = 3.1 Hz, 1H), 7.86 - 7.66 (m, 7H), 7.45 (dd, J = 14.9, 3.0 Hz, 1H), 7.37 - 7.25 (m, 4H), 7.20 - 7.12 (m, 4H), 7.09 - 7.02 (m, 4H), 6.12 (dt, J = 4.1, 2.0 Hz, 2H), 5.37 (dt, J = 4.1, 2.0 Hz, 2H), 4.61 (td, J = 15.1, 13.9 Hz, 2H), 3.87 (t, J = 15.2 Hz, 2H), 2.40 (ddd, J = 9.6, 9.1, 7.8 Hz, 4H), 1.58 - 1.12 (m, 8H), 0.93 (t, J = 12.7 Hz, 6H).

[0126] 50.0 g (0.05 mol) of compound (3-4) and 16.4 (0.1 mol) of methylbutylbenzylamine (3-5) were dissolved in 500 mL of ethanol-water (1:1 by volume) mixed solution, and reacted at 90°C overnight. After concentration under reduced pressure, 56.7 g of the target compound Y-3 was obtained. 1 H NMR (500 MHz, Chloroform) δ 8.36 (d, J = 3.1 Hz, 1H), 8.31 (s, 1H), 8.00 (dd, J = 15.0, 2.9 Hz, 1H), 7.95 (d, J = 3.1 Hz, 1H), 7.86 - 7.66 (m, 7H), 7.45 (dd, J = 14.9, 3.0 Hz, 1H), 7.37 - 7.25 (m, 4H), 7.20 - 7.12 (m, 4H), 7.09 - 7.02 (m, 4H), 6.12 (dt, J = 4.1, 2.0 Hz, 2H), 5.37 (dt, J = 4.1, 2.0 Hz, 2H), 4.61 (td, J = 15.1, 13.9 Hz, 2H), 3.87 (t, J = 15.2 Hz, 2H), 2.40 (ddd, J = 9.6, 9.1, 7.8 Hz, 4H), 1.58 - 1.12 (m, 8H), 0.93 (t, J = 12.7 Hz, 6H).

[0127] Example 4 Synthesis of polymerizable aqueous photoinitiator Y-4, the principle is shown in the following formula:

[0128]

[0129] 171 g (1 mol) of p-bromophenol (4-1) was dissolved in 1 L of dichloromethane, 175.9 g (1.2 mol) of isobutyl acryloyl chloride was added dropwise at room temperature, and stirring was continued at room temperature for 4 h after the dropwise addition was completed. The reaction was quenched with ice water, washed with saturated aqueous sodium bicarbonate solution 3 times, and dried and concentrated to obtain 239.5 g of the intermediate compound (4-3).1H NMR (500 MHz, Chloroform) δ 7.67-7.37 (m, 2H), 7.34-6.99 (m, 2H), 6.12 (dt, J = 4.1, 1.9 Hz, 1H), 5.37 (dt, J = 4.0, 1.9 Hz, 1H), 2.46 (dt, J = 14.4, 1.9 Hz, 2H), 1.88 (ddq, J = 25.2, 14.3, 12.7 Hz, 1H), 0.90 (d, J = 12.5 Hz, 6H).

[0130] 59.5 g (0.1 mol) of the intermediate compound (10) was heated and stirred at 140°C for 12 h under nitrogen in the presence of 84.9 g (0.3 mol) of compound (4-3), 97.5 g (0.3 mol) of cesium carbonate, and 500 mL of dimethyl sulfoxide. After cooling to room temperature, 1 L of water was added, and extraction was performed 3 times with dichloromethane. The dichloromethane layer was washed 5 times with water. After drying and concentration, column chromatography was performed with dichloromethane and petroleum ether to obtain 135.1 g of the intermediate compound (4-4). 1 H NMR (500 MHz, Chloroform) δ 8.36 (d, J = 2.9 Hz, 1H), 8.31 (s, 1H), 8.04-7.95 (m, 2H), 7.84 (d, J = 2.9 Hz, 1H), 7.82-7.66 (m, 6H), 7.45 (dd, J = 15.0, 3.1 Hz, 1H), 7.36-7.23 (m, 4H), 7.19-7.11 (m, 4H), 7.11-6.99 (m, 4H), 6.12 (dt, J = 4.1, 1.9 Hz, 2H), 5.37 (dt, J = 4.0, 1.9 Hz, 2H), 4.62 (td, J = 15.1, 8.2 Hz, 2H), 3.89 (t, J = 15.1 Hz, 2H), 2.46 (dt, J = 14.4, 1.9 Hz, 4H), 1.89 (tt, J = 27.1, 7.2 Hz, 2H), 0.90 (d, J = 12.5 Hz, 12H).

[0131] 50.0 g (0.05 mol) of compound (4-4) and 16.4 (0.1 mol) of methylbutylbenzylamine (3-5) were dissolved in 500 mL of ethanol-water (1:1 by volume) mixed solution, and reacted at 90°C overnight. Concentration under reduced pressure gave 59.6 g of the target compound Y-4. 1 HNMR (500 MHz, Chloroform) δ 8.36 (d, J = 1.4 Hz, 1H), 8.31 (s, 1H), 8.07 (d, J = 1.4 Hz, 1H), 8.00 (dd, J = 7.5, 1.4 Hz, 1H), 7.80 (ddd, J = 9.4, 6.2, 2.7 Hz, 3H), 7.75 - 7.67 (m, 4H), 7.45 (dd, J = 7.5, 1.4 Hz, 1H), 7.35 - 7.25 (m, 4H), 7.25 - 7.18 (m, 5H), 7.15 (d, J = 7.5 Hz, 4H), 7.06 (d, J = 7.5 Hz, 4H), 6.31 - 5.93 (m, 2H), 5.49 - 5.25 (m, 2H), 4.77 (s, 2H), 4.59 (dt, J = 17.0, 7.2 Hz, 2H), 3.69 (t, J = 7.2 Hz, 2H), 3.50 - 3.20 (m, 5H), 2.46 (d, J = 7.1 Hz, 4H), 2.02 - 1.72 (m, 4H), 1.24 (dt, J = 7.7, 7.2 Hz, 2H), 0.89 (dd, J = 8.3, 6.5 Hz, 15H).

[0132] Example 5. Synthesis of D-5, a polymerizable aqueous photoinitiator, according to the following scheme:

[0133]

[0134] 44.4 g (0.05 mol) of compound (14) and 25.3 (0.1 mol) of methyl dibenzylamine (5-1) were dissolved in 500 mL of ethanol-water (1:1 by volume) mixed solution, and reacted at 90°C overnight. Concentration under reduced pressure gave 63.4 g of the target compound Y-5. 1HNMR (500 MHz, Chloroform) δ 8.36 (d, J = 2.9 Hz, 1H), 8.31 (s, 1H), 8.15 - 7.89 (m, 2H), 7.86 - 7.59 (m, 7H), 7.54 - 6.91 (m, 23H), 6.17 (ddd, J = 52.9, 26.5, 12.4 Hz, 4H), 5.77 (d, J = 4.8 Hz, 1H), 5.70 (d, J = 4.9 Hz, 1H), 4.85 (s, 4H), 4.63 (td, J = 14.6, 7.9 Hz, 2H), 3.69 (t, J = 14.6 Hz, 2H), 3.40 (t, J = 15.2 Hz, 2H), 1.88 (p, J = 15.3 Hz, 2H), 1.44 - 1.09 (m, 2H), 0.89 (dd, J = 13.4, 12.8 Hz, 3H).

[0135] Example 6 Synthesis of Y-6, a polymerizable aqueous photoinitiator, is shown in the scheme below:

[0136]

[0137] 45.8 g (0.05 mol) of compound (2-4) and 25.3 (0.1 mol) of methyldibenzylamine (6-1) were dissolved in 500 mL of ethanol-water (1 : 1) mixture and reacted at 90 °C overnight. The target compound Y-6 was obtained by concentration under reduced pressure to give 57.4 g. 1 H NMR (500 MHz, Chloroform) δ 8.36 (s, 1H), 8.31 (s, 1H), 8.00 (d, J = 3.8 Hz, 2H), 7.85 (s, 1H), 7.79 (s, 2H), 7.72 (t, J = 5.0 Hz, 4H), 7.45 (s, 1H), 7.26 (dd, J = 35.0, 15.0 Hz, 14H), 7.15 (s, 4H), 7.06 (s, 4H), 6.43 (s, 2H), 6.18 (s, 2H), 4.77 (s, 4H), 4.72 (s, 1H), 4.60 (s, 1H), 3.69 (s, 2H), 3.40 (s, 2H), 2.01 (s, 6H), 1.88 (s, 2H), 1.25 (s, 2H), 0.89 (s, 3H).

[0138] Example 7 Synthesis of Y-7, a polymerizable aqueous photoinitiator, is shown in the scheme below:

[0139]

[0140] 50.0 g (0.05 mol) of compound (3-4) and 25.3 (0.1 mol) of methyldibenzylamine (7-1) were dissolved in 500 mL of ethanol-water (1:1 by volume) mixture and reacted at 90°C overnight. The target compound Y-7 was obtained by concentration under reduced pressure to give 52.4 g. 1 HNMR (500 MHz, Chloroform) δ 8.36 (d, J = 1.4 Hz, 1H), 8.31 (s, 1H), 8.00 (dd, J = 7.5, 1.4 Hz, 1H), 7.89 (d, J = 1.4 Hz, 1H), 7.85 (d, J = 1.5 Hz, 1H), 7.82 - 7.76 (m, 2H), 7.75 - 7.67 (m, 4H), 7.45 (dd, J = 7.5, 1.4 Hz, 1H), 7.31 (ddd, J = 19.2, 11.4, 5.7 Hz, 4H), 7.26 - 7.18 (m, 10H), 7.15 (d, J = 7.5 Hz, 4H), 7.06 (d, J = 7.5 Hz, 4H), 6.20 - 6.02 (m, 2H), 5.43 - 5.30 (m, 2H), 5.15 (s, 4H), 4.69 (t, J = 7.5 Hz, 1H), 4.56 (t, J = 7.5 Hz, 1H), 3.69 (t, J = 7.5 Hz, 2H), 3.40 (t, J = 7.7 Hz, 2H), 2.52 - 2.28 (m, 4H), 1.87 (p, J = 7.8 Hz, 2H), 1.49 - 1.13 (m, 10H), 0.91 (dt, J = 20.1, 6.6 Hz, 9H).

[0141] Example 8. Synthesis of Y-8, a polymerizable aqueous photoinitiator, whose principle is shown in the following formula:

[0142]

[0143] 50.0 g (0.05 mol) of compound (3-4) and 25.3 (0.1 mol) of methyldibenzylamine (7-1) were dissolved in 500 mL of ethanol-water (1:1 by volume) mixture and reacted at 90°C overnight. The target compound Y-7 was obtained by concentration under reduced pressure to give 52.4 g. 1HNMR (500 MHz, Chloroform) δ 8.36 (d, J = 2.9 Hz, 1H), 8.31 (s, 1H), 8.12 (d, J = 2.9 Hz, 1H), 8.00 (dd, J = 15.0, 2.9 Hz, 1H), 7.84 - 7.67 (m, 6H), 7.64 (d, J = 2.9 Hz, 1H), 7.45 (dd, J = 14.9, 3.0 Hz, 1H), 7.37 - 7.19 (m, 14H), 7.18 - 7.11 (m, 4H), 7.10 - 7.01 (m, 4H), 6.12 (dt, J = 4.1, 2.0 Hz, 2H), 5.37 (dt, J = 4.1, 2.0 Hz, 2H), 4.93 (s, 4H), 4.44 (td, J = 8.5, 5.7 Hz, 2H), 3.69 (t, J = 8.6 Hz, 2H), 3.40 (t, J = 15.4 Hz, 2H), 2.46 (dt, J = 14.5, 1.9 Hz, 4H), 2.06 - 1.69 (m, 4H), 1.37 - 1.10 (m, 2H), 0.89 (t, J = 12.4 Hz, 15H).

[0144] Example 9. Synthesis of Y-9, a polymerizable aqueous photoinitiator, according to the following scheme:

[0145]

[0146] 44.4 g (0.05 mol) of compound (14) and 10.1 (0.1 mol) of dimethylbutylamine (9-1) were dissolved in 500 mL of ethanol-water (1:1 by volume) mixture and reacted at 90 °C overnight. The target compound Y-9 was obtained by concentration under reduced pressure to give 41.2 g. 1HNMR (500 MHz, Chloroform) δ 8.36 (d, J = 2.9 Hz, 1H), 8.31 (s, 1H), 8.05 - 7.93 (m, 2H), 7.86 - 7.66 (m, 7H), 7.45 (dd, J = 15.0, 2.9 Hz, 1H), 7.37 - 7.23 (m, 4H), 7.20 - 7.11 (m, 4H), 7.09 - 7.01 (m, 4H), 6.26 (d, J = 4.8 Hz, 1H), 6.22 (d, J = 4.8 Hz, 1H), 6.13 (d, J = 20.0 Hz, 1H), 6.07 (d, J = 20.0 Hz, 1H), 5.77 (d, J = 4.8 Hz, 1H), 5.70 (d, J = 4.8 Hz, 1H), 4.65 (t, J = 13.5 Hz, 1H), 4.48 (t, J = 13.5 Hz, 1H), 3.69 (t, J = 13.5 Hz, 2H), 3.40 (t, J = 15.6 Hz, 2H), 3.34 (s, 6H), 1.84 (tt, J = 15.6, 10.4 Hz, 2H), 1.25 (tdd, J = 4.0, 3.2, 1.9 Hz, 2H), 0.89 (t, J = 13.1 Hz, 3H).

[0147] Example 10. Synthesis of Y-10, a polymerizable aqueous photoinitiator, according to the following scheme:

[0148]

[0149] 45.8 g (0.05 mol) of compound (2-4) and 10.1 (0.1 mol) of dimethylbutylamine (10-1) were dissolved in 500 mL of ethanol-water (1:1 by volume) mixture and reacted at 90 °C overnight. The target compound Y-10 was obtained by concentration under reduced pressure to give 48.7 g. 1H NMR (500 MHz, Chloroform) δ 8.36 (d, J = 1.4 Hz, 1H), 8.31 (s, 1H), 8.00 (dd, J = 7.5, 1.4 Hz, 1H), 7.89 (d, J = 1.4 Hz, 1H), 7.83 - 7.75 (m, 3H), 7.75 - 7.66 (m, 4H), 7.45 (dd, J = 7.5, 1.4 Hz, 1H), 7.32 (dd, J = 5.5, 3.5 Hz, 2H), 7.28 (d, J = 7.5 Hz, 2H), 7.15 (d, J = 7.5 Hz, 4H), 7.06 (d, J = 7.5 Hz, 4H), 6.51 - 6.30 (m, 2H), 6.24 - 6.07 (m, 2H), 4.59 (t, J = 7.5 Hz, 1H), 4.53 (t, J = 7.5 Hz, 1H), 3.69 (t, J = 7.5 Hz, 2H), 3.45 (s, 6H), 3.40 (t, J = 7.8 Hz, 2H), 2.01 (s, 6H), 1.83 (p, J = 7.8 Hz, 2H), 1.40 - 1.11 (m, 2H), 0.89 (t, J = 6.6 Hz, 3H).

[0150] Example 11. Synthesis of Y-11, a polymerizable aqueous photoinitiator, according to the following scheme:

[0151]

[0152] 50.0 g (0.05 mol) of compound (3-4) and 10.1 (0.1 mol) of dimethylbutylamine (11-1) were dissolved in 500 mL of ethanol-water (1:1 by volume) mixture and reacted at 90 °C overnight. The target compound Y-11 was obtained by concentration under reduced pressure to give 47.8 g. 1H NMR (500 MHz, Chloroform) δ 8.36 (d, J = 2.9 Hz, 1H), 8.31 (s, 1H), 8.00 (dd, J = 15.0, 2.9 Hz, 1H), 7.94 (d, J = 3.0 Hz, 1H), 7.84 (t, J = 4.9 Hz, 1H), 7.82 - 7.65 (m, 6H), 7.45 (dd, J = 15.0, 3.1 Hz, 1H), 7.37 - 7.23 (m, 4H), 7.20 - 7.11 (m, 4H), 7.09 - 7.01 (m, 4H), 6.12 (dt, J = 4.1, 1.9 Hz, 2H), 5.37 (dt, J = 4.0, 1.9 Hz, 2H), 4.54 (dt, J = 18.1, 15.1 Hz, 2H), 3.69 (t, J = 15.0 Hz, 2H), 3.40 (t, J = 15.6 Hz, 2H), 3.26 (s, 6H), 2.55 - 2.26 (m, 4H), 2.02 - 1.66 (m, 2H), 1.53 - 1.07 (m, 10H), 0.91 (ddd, J = 20.4, 12.9, 9.1 Hz, 9H).

[0153] Example 12. Synthesis of Y-12, a polymerizable aqueous photoinitiator, according to the following scheme:

[0154]

[0155] 50.0 g (0.05 mol) of compound (4-4) and 10.1 (0.1 mol) of dimethylbutylamine (12-1) were dissolved in 500 mL of ethanol-water (1:1 by volume) mixture and reacted at 90 °C overnight. The target compound Y-12 was obtained by concentration under reduced pressure to give 41.8 g. 1H NMR (500 MHz, Chloroform) δ 8.36 (d, J = 1.4 Hz, 1H), 8.31 (s, 1H), 8.05 - 7.95 (m, 2H), 7.79 (dd, J = 5.2, 3.7 Hz, 3H), 7.75 - 7.66 (m, 4H), 7.45 (dd, J = 7.5, 1.4 Hz, 1H), 7.34 - 7.30 (m, 2H), 7.28 (d, J = 7.5 Hz, 2H), 7.15 (d, J = 7.5 Hz, 4H), 7.06 (d, J = 7.5 Hz, 4H), 6.23 - 5.86 (m, 2H), 5.51 - 5.21 (m, 2H), 4.63 (t, J = 7.5 Hz, 1H), 4.57 (t, J = 7.4 Hz, 1H), 3.69 (t, J = 7.5 Hz, 2H), 3.40 (t, J = 7.8 Hz, 2H), 3.34 (s, 6H), 2.46 (d, J = 7.3 Hz, 4H), 2.04 - 1.66 (m, 4H), 1.25 (td, J = 7.8, 3.9 Hz, 2H), 0.89 (dd, J = 8.3, 6.5 Hz, 15H).

[0156] Detection and experimental verification

[0157] Migration test: A mixture with mass ratio of photoinitiator: dichloromethane: trimethylolpropane triacrylate = 2:5:98 was evenly spread in a 250 mL flat-bottomed conical flask, the conical flask was evacuated three times with nitrogen and irradiated with a 390 nm LED point light source for 10 min to ensure complete curing. The cured film was removed and ground into powder. The cured film powder was weighed and placed in 10 mL of acetonitrile and stirred for 48 h, then filtered, and the filtrate was diluted to 10 mL. The absorbance of the test solution was tested, and according to the Lambert-Beer law, the migration rate was calculated according to the following formula:

[0158]

[0159] where A is the absorbance at the maximum absorption wavelength of the photoinitiator, M r is the relative molecular mass of the photoinitiator, ε is the molar extinction coefficient at the maximum absorption wavelength, l is the length of the absorption cell (1 cm), and m0 is the mass of the cured film powder.

[0160] The migration rates of the polymerizable aqueous photoinitiators Y-1 to 12 are shown in Table 1. As can be seen from the data in Table 1, the migration rate of the polymerizable aqueous photoinitiator prepared in the present application is small.

[0161] Table 1 Migration rates of polymerizable aqueous photoinitiators Y-1 to 12

[0162] Photoinitiator Mobility Photoinitiator Mobility Competitor TPOs 0.51％ Y-7 0.04％ Y-1 0.01％ Y-8 0％ Y-2 0％ Y-9 0％ Y-3 0％ Y-10 0％ Y-4 0.02％ Y-11 0.01％ Y-5 0％ Y-12 0％ Y-6 0.01％

[0163] Double bond conversion rate: 1wt% initiator was added into the monomer trimethylolpropane triacrylate and stirred uniformly; a drop of the mixture was spread evenly on a piece of potassium bromide salt, and a thin and transparent layer of potassium bromide salt was covered on the upper surface to prevent oxygen inhibition. The double bond conversion rate was tested by Fourier transform real-time infrared spectrometer Nicolet iS50 with LED point light source with wavelength of 390 nm and 430 nm. The double bond conversion rates of Y-1-12 of the polymerizable aqueous photoinitiator are shown in Table 2. From the data in Table 2, it can be seen that the double bond conversion rate of the polymerizable aqueous photoinitiator prepared by the present application is high.

[0164] Table 2 Double bond conversion rate of polymerizable aqueous photoinitiator

[0165]

[0166]

[0167] The above description is only preferred embodiments of the present application, and does not limit the present application in any form. It should be noted that for those skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A polymerizable aqueous photoinitiator, characterized in that, has any one of structures Y1-Y12: 。 2. Process for the preparation of polymerizable aqueous photoinitiators according to claim 1, characterized in that, comprising the following steps: carbazole-1-formaldehyde, hydroxylamine hydrochloride, sodium acetate and a solvent are mixed to perform a nucleophilic addition reaction to obtain a carbazole formaldehyde oxime; the carbazole formaldehyde oxime, benzothiophene carboxylic acid, dicyclohexyl carbodiimide and an organic solvent are mixed to perform a dehydration reaction to obtain an intermediate compound; the intermediate compound has a structure shown in formula E; the intermediate compound, a terminal dibromo-substituted alkane and an organic solvent are mixed to perform a first substitution reaction to obtain a first substitution product; the first substitution product has a structure shown in formula G; the terminal dibromo-substituted alkane has a structure shown in formula F; the first substitution product, anhydrous aluminum chloride, p-nitrobenzoyl chloride and an organic solvent are mixed to perform a Friedel-Crafts acylation reaction to obtain a Friedel-Crafts acylation product; the Friedel-Crafts acylation product has a structure shown in formula I; the Friedel-Crafts acylation product, iron powder, an aqueous ammonium chloride solution and an organic solvent are mixed to perform a reduction reaction to obtain a reduction product; the reduction product has a structure shown in formula J; p-bromophenol, acryloyl chloride and an organic solvent are mixed to perform a second substitution reaction to obtain a second substitution product; the second substitution product has a structure shown in formula M; the reduction product, the second substitution product, anhydrous cesium carbonate and an organic solvent are mixed to perform a third substitution reaction to obtain a third substitution product; the third substitution product has a structure shown in formula P; the third substitution product and an amine substance are mixed to perform a nucleophilic substitution reaction to obtain a nucleophilic substitution product; the amine substance has a structure shown in formula Q; the nucleophilic substitution product and a sodium salt are mixed to perform ion exchange to obtain the polymerizable water-based photoinitiator; the principle of the preparation method is shown in the following formula: the substituents in the compound having the structure shown in formula Y are consistent with the substituents in the compound having any one of structures Y1-Y12 in claim 1, and the definition of each substituent in the compound having the structure shown in formula Y is consistent with the definition of each corresponding substituent in the raw material.

3. The preparation method according to claim 2, characterized in that, the molar ratio of the carbazole-1-formaldehyde to the hydroxylamine hydrochloride is 1:

2.

4. The production method according to claim 2, characterized by, the molar ratio of the intermediate compound to the terminal dibromo-substituted alkane is 4:

5.

5. The preparation method according to claim 2, characterized in that, the molar ratio of the first substitution product to the p-nitrobenzoyl chloride is 3:

5.

6. The preparation method according to claim 2, characterized in that, the molar ratio of the p-bromophenol to the acryloyl chloride is 1:1.

2.

7. The preparation method according to claim 2, characterized in that, the molar ratio of the third substitution product to the amine substance is 1:

2.

8. The preparation method according to claim 2, characterized in that, the temperature of the reduction reaction is 80-90°C, and the time is 10-24h.

9. Application of the polymerizable water-based photoinitiator in claim 1 as an initiator for photocuring coatings.

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