BENZOPHENONE DERIVATIVE, METHOD FOR PREPARING SAME, AND USE THEREOF

Abstract

The present application relates to a benzophenone derivative, a method for preparing same, and use thereof. The benzophenone derivative has a structure represented by formula (1), formula (2), or formula (3). Compared with EMK, the bis(dialkylamino)benzophenone compound with an acrylate group side chain provided by the present application has a remarkably increased molecular weight and contains a polymerizable double bond, showing remarkably lower mobility in a cured film and thus being applicable in the fields of food packaging, printing formulations, and the like.

##STR00001##

Claims

1. A benzophenone derivative, wherein the benzophenone derivative has a structure represented by formula (1): ##STR00074## wherein: n.sub.1 is an integer from 1 to 10, R.sub.1 is an optionally substituted C1-C8 alkyl, R.sub.2 is H or CH.sub.3, R.sub.3 is H or ##STR00075## G.sub.1 is an optionally substituted C1-C12 alkylene, ##STR00076## m.sub.1 is an integer from 1 to 11, and m.sub.2 is an integer from 1 to 12.

2. The benzophenone derivative of claim 1, wherein n.sub.1 is an integer from 1 to 4; preferably, R.sub.1 is a C1-C4 alkyl, further preferably-CH.sub.2CH.sub.3; preferably, R.sub.2 is H; preferably, R.sub.3 is ##STR00077## R.sub.2 and G.sub.1 have the same definitions as those in formula (1) of claim 1; and preferably, G.sub.1 is CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2CH.sub.2 or CH.sub.2CH.sub.2OCH.sub.2CH.sub.2.

3. A benzophenone derivative, wherein the benzophenone derivative has a structure represented by formula (2): ##STR00078## wherein: n.sub.2 is an integer from 1 to 10, R.sub.1 is an optionally substituted C1-C8 alkyl, R.sub.2 is H or CH.sub.3, R.sub.4 is H or ##STR00079## G.sub.2 is an optionally substituted C1-C12 alkylene or ##STR00080## and m.sub.3 is an integer from 1 to 11.

4. The benzophenone derivative of claim 3, wherein n.sub.2 is an integer from 1 to 6; preferably, R.sub.1 is preferably a C1-C4 alkyl, further preferably-CH.sub.2CH.sub.3; preferably, R.sub.2 is H; preferably, R.sub.4 is ##STR00081## the R.sub.2 and G.sub.2 have the same definitions as those in formula (2) of claim 3.

5. A benzophenone derivative, wherein the benzophenone derivative has a structure represented by formula (3): ##STR00082## wherein: n.sub.3 is an integer from 1 to 10, R.sub.1 is an optionally substituted C1-C8 alkyl, R.sub.2 is H or CH.sub.3, R.sub.5 is H or ##STR00083## G.sub.2 is an optionally substituted C1-C12 alkylene or ##STR00084## m.sub.3 is an integer from 1 to 11; G.sub.3 is an optionally substituted C1-C12 alkylene, ##STR00085## and m.sub.4 is an integer from 1 to 11.

6. The benzophenone derivative of claim 5, wherein n.sub.3 is an integer from 1 to 6; preferably, R.sub.1 is a C1-C4 alkyl, further preferably-CH.sub.2CH.sub.3; preferably, R.sub.2 is H; preferably, R.sub.5 is ##STR00086## the R.sub.2, G.sub.2 and G.sub.3 have the same definitions as those in formula (3) of claim 5; and preferably, G.sub.2 and G.sub.3 are each independently CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH.sub.2OCH.sub.2CH.sub.2 or CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2.

7. A method for preparing the benzophenone derivative of claim 1, comprising: performing a reaction between the compound represented by formula (4) and the compound represented by formula (5) until at least one of the hydroxyl groups at both ends of the compound represented by formula (4) is fully added, and then ending the reaction to obtain a benzophenone derivative with the structure of formula (1); ##STR00087## wherein a molar ratio of the compound represented by formula (4) to the compound represented by formula (5) is in a range from 1:1 to 1:2, and R.sub.1, R.sub.2 and G.sub.1 have the same definitions as those in formula (1).

8. The method of claim 7, wherein the reaction temperature is in a range from 40 C. to 120 C. and the reaction time is in a range from 10 h to 100 h.

9. The method for preparing the benzophenone derivative of claim 3, comprising: performing a reaction between the compound represented by formula (6) and the compound represented by formula (7) until at least one of the hydroxyl groups at both ends of the compound represented by formula (6) is fully added, adding the compound represented by formula (8) and continuing to react until the content of the compound represented by equation (8) no longer decreases, and stopping the reaction; ##STR00088## wherein a molar ratio of the compound represented by formula (6) to the compound represented by formula (7) is in a range from 1:1 to 1:2, and a molar ratio of the compound represented by formula (6) to the compound represented by formula (8) is in a range from 1:0.5 to 1:3, and R.sub.1, R.sub.2 and G.sub.2 have the same definitions as those in formula (2).

10. The method of claim 9, wherein the reaction temperature is in a range from 40 C. to 120 C. and the reaction time is in a range from 10 h to 100 h.

11. A method for preparing benzophenone derivatives of claim 5, comprising: performing a reaction the compound represented by formula (9) with the compound represented by formula (10) until at least one of the hydroxyl groups at both ends of the compound represented by formula (9) is fully added, then adding the compound represented by formula (11), and continuing to react until all double bonds in the vinyl of the compound represented by formula (11) are added; ##STR00089## wherein a molar ratio of the compound represented by formula (9) and the compound represented by formula (10) is 1:1 to 1:2, and the molar ratio of the compound represented by formula (9) and the compound represented by formula (11) is 1:1 to 1:3, and R.sub.1, R.sub.2, G.sub.2 and G.sub.3 have the same definitions as those in formula (3).

12. The method of claim 11, wherein the reaction temperature is in a range from 40 C. to 120 C. and the reaction time is in a range from 10 h to 100 h.

13. A photoinitiator composition, wherein the photoinitiator composition comprises a photoinitiator for free radical polymerization and the benzophenone derivative of claim 1.

14. A photocurable composition, wherein the photocurable composition comprises a photoinitiator component and a radically polymerizable ethylenically unsaturated compound, and the photoinitiator component comprises the photoinitiator composition of claim 13.

15. The photocurable composition of claim 14, wherein the photocurable composition comprises: (a) the benzophenone derivative; (b) a photoinitiator for free radical polymerization; and (c) a free-radically polymerizable ethylenically unsaturated compound; wherein the benzophenone derivative has a structure represented by formula (1): ##STR00090## wherein: n.sub.1 is an integer from 1 to 10, R.sub.1 is an optionally substituted C1-C8 alkyl, R.sub.2 is H or CH.sub.3, R.sub.3 is H or ##STR00091## G.sub.1 is an optionally substituted C1-C12 alkylene, ##STR00092## m.sub.1 is an integer from 1 to 11, and m.sub.2 is an integer from 1 to 12.

16. The photocurable composition of claim 15, wherein the component (a) is added in an amount ranging from from 0.1% to 20% of the total weight of the photocurable composition; or the component (b) is added in an amount ranging from 0.1% to 10% of the total weight of the photocurable composition; or wherein the component (b) is selected from the group consisting of benzophenones, thioxanthone compounds, -hydroxyketone compounds, -aminoketones compounds, acyl phosphine oxide compounds, oxime lipid compounds, and any combination thereof; preferably, at least one of benzophenone, 2-isopropylthiaxanthone, 2-dimethylamino-2-(4-methyl benzyl)-1-(4-morpholinylphenyl)-1-butanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, photoinitiator Omnipol TX, photoinitiator Omnipol 910 and photoinitiator Omnipol TP; or the component (c) is at least one selected from the group consisting of epoxy acrylate resin, polyurethane acrylate resin, polyester acrylate resin, polyether acrylate resin, and acrylate resin, polyacrylate, epoxy methacrylate resin, polyurethane methacrylate resin, polyester methacrylate resin, polyether methacrylate resin, acrylated polymethacrylate, allyl ether compound, acrylate monomer and methacrylate monomer.

17-19. (canceled)

20. Use of the photocurable composition of claim 14 in food packaging printing, pharmaceutical packaging printing, furniture coating, book printing and advertising printing.

21. A photocurable product, wherein the photocurable product is formed by photocuring a photocurable composition, wherein the photocurable composition is the photocurable composition of claim 14.

22. A method for curing a photocurable composition, comprising coating the photocurable composition of claim 14 on a substrate; and curing the photocurable composition by using a light source with an emission band in the UV-visible light region;

23. The method of claim 22, wherein the substrate is selected from the group consisting of wood, paper, plastic, coating and metal; or the coating method is selected from the group consisting of offset printing, gravure printing, flexographic printing, inkjet printing and 3D printing; or after coating on the substrate, the photocurable composition is cured by irradiating with UV-visible light having a wavelength ranging from 200 nm to 425 nm; preferably, the photocurable composition is cured by irradiating with UV-visible light having a wavelength ranging from 365 nm to 405 nm.

24-26. (canceled)

Description

DETAILED DESCRIPTION

[0110] Experimental raw materials and materials:

TABLE-US-00001 Reagent specifications Reagents Name and content Reagent source HEMK* >98% Self made, reference: CN107434773A Butyl glycidyl ether >98% Shanghai Aladdin Bio-Chem Technology Co., LTD Ethyl glycidyl ether >98% Shanghai Aladdin Bio-Chem Technology Co., LTD Ethylene oxide >98% Shanghai Aladdin Bio-Chem Technology Co., LTD Propylene oxide >98% Shanghai Aladdin Bio-Chem Technology Co., LTD Potassium hydroxide AR Shanghai Aladdin Bio-Chem Technology Co., LTD Sodium hydroxide AR Shanghai Aladdin Bio-Chem Technology Co., LTD Anhydrous sodium AR Shanghai Aladdin Bio-Chem carbonate Technology Co., LTD Triethylamine AR Shanghai Aladdin Bio-Chem Technology Co., LTD Acetic Anhydride >98% Shanghai Aladdin Bio-Chem Technology Co., LTD Acryloyl chloride >98% Shanghai Aladdin Bio-Chem Technology Co., LTD Butyl isocyanate >98% Shanghai Aladdin Bio-Chem Technology Co., LTD 2-acryloyloxyethyl >98% Shanghai Aladdin Bio-Chem isocyanate Technology Co., LTD *The structure of HEMK is [00024]Omnipol TX is a photoinitiator of polybutylene glycol 250-bis(2-carboxy- methoxythioxanthone) ester, a product of IGM RESINS; Omnirad EMK is 4,4-bis(diethylamino)benzophenone, a product of IGM RESINS; Photomer 4072 is trimethylolpropane propoxy (3) triacrylate, a product of IGM RESINS; Photomer 3316 is a low viscosity modified epoxy acrylate, a product of IGM RESINS.

Example 1

[0111] To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 1.86 g (10 mmol) of 2-vinyloxyethoxyethyl acrylate (VEEA), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55 C. and the reaction time was 48 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. The temperature was lowered to 30 C., 3.0 g sodium carbonate aqueous solution with a mass concentration of 5% (1.4 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 3.44 g of the product of formula IX, with an effective group content of 55%. The effective group refers to the remaining residue in the HEMK structure after removing the hydrogen on the two hydroxyl groups.

##STR00025##

TABLE-US-00002 TABLE 1 Analysis results of the product of Example 1 by liquid chromatography-mass spectrometry Retention Content Molecular Value of n.sub.1 in Number time (min) (%) mass formula IX R.sub.3 in formula IX 1 3.16 1.87 542.67 1 H 2 5.87 40.36 728.88 1 [00026] 3 7.07 3.34 925.18 2 H 4 10.19 24.27 1111.38 2 [00027] 5 10.94 2.05 1307.68 3 H 6 13.08 15.08 1493.89 3 [00028] 7 13.56 1.20 1690.19 4 H 8 14.99 6.25 1876.39 4 [00029] 9 15.49 0.37 2072.7 5 H 10 16.94 3.26 2258.89 5 [00030] 11 19.52 1.31 2455.21 6 H 12 23.14 0.54 2641.39 6 [00031]

Example 2

[0112] To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 1.86 g (10 mmol) of 2-vinyloxyethoxyethyl acrylate (VEEA), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.11 mmol) of poly(4-vinylpyridine-p-toluenesulfonate) and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55 C. and the reaction time was 48 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. The temperature was lowered to 30 C., 3.0 g sodium carbonate aqueous solution with a mass concentration of 5% (1.4 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 3.40 g of the product of formula IX.

##STR00032##

TABLE-US-00003 TABLE 2 Analysis results of the product of Example 2 by liquid chromatography-mass spectrometry Retention Content Molecular Value of n.sub.1 in Number time (min) (%) mass formula IX R.sub.3 is formula IX 1 3.16 7.29 542.67 1 H 2 5.87 28.74 728.88 1 [00033] 3 7.07 5.32 925.18 2 H 4 10.19 24.57 1111.38 2 [00034] 5 10.94 2.85 1307.68 3 H 6 13.08 15.92 1493.89 3 [00035] 7 13.56 1.38 1690.19 4 H 8 14.99 7.75 1876.39 4 [00036] 9 15.49 0.42 2072.7 5 H 10 16.94 3.87 2258.89 5 [00037] 11 19.52 1.00 2455.21 6 H 12 23.14 0.88 2641.39 6 [00038]

Example 3

[0113] To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 2.00 g (10 mmol) of 2-vinyloxyethoxyethyl methacrylate (VEEM), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55 C. and the reaction time was 48 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. The temperature was lowered to 30 C., 3.0 g sodium carbonate aqueous solution with a mass concentration of 5% (1.4 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 3.51 g of the product of formula X.

##STR00039##

TABLE-US-00004 TABLE 3 Analysis results of the product of Example 3 by liquid chromatography-mass spectrometry Retention Content Molecular Value of n.sub.1 in Number time (min) (%) mass formula X R.sub.3 is formula X 1 3.12 2.58 556.69 1 H 2 5.80 38.69 756.92 1 [00040] 3 6.92 3.6 939.20 2 H 4 10.03 25.21 1139.42 2 [00041] 5 10.88 2.39 1321.70 3 H 6 12.99 16.23 1521.93 3 [00042] 7 13.32 1.27 1704.21 4 H 8 14.58 5.34 1904.43 4 [00043] 9 15.31 0.38 2086.72 5 H 10 16.72 2.85 2286.93 5 [00044] 11 18.98 1.03 2469.23 6 H 12 22.34 0.40 2669.43 6 [00045]

Example 4

[0114] To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 1.42 g (10 mmol) of 2-vinyloxyethyl acrylate (VEA), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55 C. and the reaction time was 48 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. The temperature was lowered to 30 C., 3.0 g sodium carbonate aqueous solution with a mass concentration of 5% (1.4 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 2.91 g of the product of formula XI, with an effective group content of 55%.

##STR00046##

TABLE-US-00005 TABLE 4 Analysis results of the product of Example 4 by liquid chromatography-mass spectrometry Retention Content Molecular Value of n.sub.1 in Number time (min) (%) mass formula XI R.sub.3 is formula XI 1 3.02 1.06 498.62 1 H 2 5.44 40.58 640.77 1 [00047] 3 6.85 1.58 881.12 2 H 4 9.76 25.84 1023.27 2 [00048] 5 10.14 1.36 1264.62 3 H 6 12.56 15.21 1406.77 3 [00049] 7 13.01 0.98 1647.12 4 H 8 14.25 7.65 1789.27 4 [00050] 9 14.93 0.38 2029.72 5 H 10 15.19 2.85 2171.77 5 [00051] 11 17.32 1.67 2412.22 6 H 12 20.87 0.82 2554.27 6 [00052]

Example 5

[0115] To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 1.42 g (10 mmol) of 2-vinyloxyethyl acrylate (VEA), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-toluenesulfonic acid and 12.0 g of dichloroethane were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55 C. and the reaction time was 48 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. The temperature was lowered to 30 C., 3.0 g sodium carbonate aqueous solution with a mass concentration of 5% (1.4 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 2.88 g of the product of formula XI.

##STR00053##

TABLE-US-00006 TABLE 5 Analysis results of the product of Example 5 by liquid chromatography-mass spectrometry Retention Content Molecular Value of n.sub.1 in Number time (min) (%) mass formula XI R.sub.3 is formula XI 1 3.02 0.98 498.62 1 H 2 5.44 36.86 640.77 1 [00054] 3 6.85 2.41 881.12 2 H 4 9.76 24.80 1023.27 2 [00055] 5 10.14 1.60 1264.62 3 H 6 12.56 12.87 1406.77 3 [00056] 7 13.01 1.28 1647.12 4 H 8 14.25 11.59 1789.27 4 [00057] 9 14.93 0.88 2029.72 5 H 10 15.19 3.81 2171.77 5 [00058] 11 17.32 1.59 2412.22 6 H 12 20.87 1.32 2554.27 6 [00059]

Example 6

[0116] To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 1.56 g (12 mmol) of 2-vinyloxyethyl methacrylate (VEM), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55 C. and the reaction time was 48 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. The temperature was lowered to 30 C., 3.0 g sodium carbonate aqueous solution with a mass concentration of 5% (1.4 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 3.07 g of the product of formula XII.

##STR00060##

TABLE-US-00007 TABLE 6 Analysis results of the product of Example 6 by liquid chromatography-masss spectrometry Retention Content Molecular Value of n.sub.1 in Number time (min) (%) mass formula XII R.sub.3 is formula XII 1 3.15 1.38 512.64 1 H 2 5.94 39.89 654.79 1 [00061] 3 7.26 1.20 895.14 2 H 4 10.55 26.66 1037.29 2 [00062] 5 10.94 1.28 1278.64 3 H 6 13.20 16.38 1420.79 3 [00063] 7 14.32 0.70 1661.14 4 H 8 15.00 7.49 1803.29 4 [00064] 9 15.93 0.78 2043.64 5 H 10 17.49 2.42 2185.79 5 [00065] 11 19.32 1.32 2426.14 6 H 12 21.87 0.49 2568.29 6 [00066]

Example 7

[0117] To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 1.58 g (10 mmol) of diethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55 C. and the reaction time was 48 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. Then 0.86 g (12 mmol) of acrylic acid was added, and continue to stir for reaction under heat preservation. A sample was taken for testing every 4 hours of reaction time. The reaction was stopped until the acrylic acid content no longer decreases. The temperature was lowered to 30 C., 6.4 g sodium carbonate aqueous solution with a mass concentration of 5% (3.0 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 3.91 g of the product of formula XIII, with an effective group content of 40%.

##STR00067##

TABLE-US-00008 TABLE 7 Analysis results of the product of Example 7 by liquid chromatography-mass spectrometry Retention time Value of n.sub.2 Number (min) Content (%) Molecular mass in formula XIII 1 7.20 19.44 816.99 1 2 11.17 20.86 1331.66 2 3 13.92 16.51 1846.24 3 4 15.67 12.89 2360.91 4 5 17.88 9.03 2875.58 5 6 19.76 8.24 3390.25 6 7 22.80 5.33 3904.92 7 8 25.93 3.66 4419.59 8 9 27.62 2.58 4934.26 9 10 30.77 1.55 5448.93 10

Example 8

[0118] To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 0.99 g (6.25 mmol) of diethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55 C. and the reaction time was 72 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. Then 0.22 g (3 mmol) of acrylic acid was added, and continued to stir for reaction under heat preservation. A sample was taken for testing every 4 hours of reaction time. The reaction was stopped until the acrylic acid content no longer decreases. The temperature was lowered to 30 C., 6.4 g sodium carbonate aqueous solution with a mass concentration of 5% (3.0 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 2.58 g of the product of formula XIII.

##STR00068##

TABLE-US-00009 TABLE 8 Analysis results of the product of Example 8 by liquid chromatography-mass spectrometry Retention time Value of n.sub.2 Number (min) Content (%) Molecular mass in formula XIII 1 7.20 17.15 816.99 1 2 11.17 8.06 1331.66 2 3 13.92 14.51 1846.24 3 4 15.67 14.40 2360.91 4 5 17.88 16.04 2875.58 5 6 19.76 13.04 3390.25 6 7 22.80 8.82 3904.92 7 8 25.93 5.30 4419.59 8 9 27.62 2.05 4934.26 9 10 30.77 0.62 5448.93 10

Example 9

[0119] To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 1.58 g (10 mmol) of diethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55 C. and the reaction time was 48 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. Then 1.39 g (12 mmol) of hydroxyethyl acrylate was added, and continued to stir for reaction under heat preservation. A sample was taken for testing every 4 hours of reaction time. The reaction was stopped until the hydroxyethyl acrylate content no longer decreases. The temperature was lowered to 30 C., 6.4 g sodium carbonate aqueous solution with a mass concentration of 5% (3.0 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 4.15 g of the product of formula XIV, with an effective group content of 40%.

##STR00069##

TABLE-US-00010 TABLE 9 Analysis results of the product of Example 9 by liquid chromatography-mass spectrometry Retention time Value of n.sub.3 Number (min) Content (%) Molecular mass in formula XIV 1 7.28 20.54 905.09 1 2 11.38 21.85 1419.76 2 3 14.00 17.06 1934.43 3 4 15.96 12.44 2449.10 4 5 18.04 9.06 2963.77 5 6 20.39 7.92 3478.44 6 7 23.09 4.83 3993.11 7 8 26.60 3.55 4507.78 8 9 28.51 2.18 5022.45 9 10 31.63 1.55 5537.12 10

Example 10

[0120] To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 0.99 g (6.25 mmol) of diethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55 C. and the reaction time was 72 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. Then 0.35 g (3 mmol) of hydroxyethyl acrylate was added, and continued to stir for reaction under heat preservation. A sample was taken for testing every 4 hours of reaction time. The reaction was stopped until the hydroxyethyl acrylate content no longer decreases. The temperature was lowered to 30 C., 6.4 g sodium carbonate aqueous solution with a mass concentration of 5% (3.0 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 2.74 g of the product of formula XIV.

##STR00070##

TABLE-US-00011 TABLE 10 Analysis results of the product of Example 10 by liquid chromatography-mass spectrometry Retention time Value of n.sub.3 Number (min) Content (%) Molecular mass in formula XIV 1 7.28 17.15 905.09 1 2 11.38 8.06 1419.76 2 3 14.00 14.51 1934.43 3 4 15.96 14.43 2449.10 4 5 18.04 16.24 2963.77 5 6 20.39 11.79 3478.44 6 7 23.09 7.76 3993.11 7 8 26.60 5.34 4507.78 8 9 28.51 3.19 5022.45 9 10 31.63 1.51 5537.12 10

Example 11

[0121] To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 2.02 g (10 mmol) of triethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55 C. and the reaction time was 48 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. Then 1.39 g (12 mmol) of hydroxyethyl acrylate was added, and continued to stir for reaction under heat preservation. A sample was taken for testing every 4 hours of reaction time. The reaction was stopped until the hydroxyethyl acrylate content no longer decreases. The temperature was lowered to 30 C., 6.4 g sodium carbonate aqueous solution with a mass concentration of 5% (3.0 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 4.66 g of the product of formula XV, with an effective group content of 40%

##STR00071##

TABLE-US-00012 TABLE 11 Analysis results of the product of Example 11 by liquid chromatography-mass spectrometry Retention time Value of n.sub.3 Number (min) Content (%) Molecular mass in formula XV 1 7.45 21.42 993.20 1 2 11.83 22.03 1551.91 2 3 15.52 17.45 2110.63 3 4 1677 12.33 2669.35 4 5 18.91 8.60 3228.07 5 6 21.16 7.61 3786.79 6 7 24.42 4.38 4345.51 7 8 27.88 3.11 4904.23 8 9 29.33 2.08 5462.95 9 10 33.55 0.98 6021.67 10

Example 12

[0122] To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 1.26 g (6.25 mmol) of triethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55 C. and the reaction time was 96 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. Then 0.35 g (3 mmol) of hydroxyethyl acrylate was added, and continued to stir for reaction under heat preservation. A sample was taken for testing every 4 hours of reaction time. The reaction was stopped until the hydroxyethyl acrylate content no longer decreases. The temperature was lowered to 30 C., 6.4 g sodium carbonate aqueous solution with a mass concentration of 5% (3.0 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 3.06 g of the product of formula XV.

##STR00072##

TABLE-US-00013 TABLE 12 Analysis results of the product of Example 12 by liquid chromatography-mass spectrometry Retention time Value of n.sub.3 Number (min) Content (%) Molecular mass in formula XV 1 7.45 18.67 993.20 1 2 11.83 19.63 1551.91 2 3 15.52 20.13 2110.63 3 4 1677 15.53 2669.35 4 5 18.91 8.80 3228.07 5 6 21.16 6.61 3786.79 6 7 24.42 4.38 4345.51 7 8 27.88 3.11 4904.23 8 9 29.33 1.99 5462.95 9 10 33.55 1.14 6021.67 10

Example 13

[0123] To a 100 mL three-necked flask with mechanical stirrer, 1.78 g (5 mmol) of HEMK, 1.42 g (10 mmol) of 1,4-butanediol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement under room temperature with stirring, the mixture was heated and stirred for reaction under the nitrogen balloon sealing. The reaction temperature was 55 C. and the reaction time was 48 hours. A sample was taken for HPLC detection and the reaction was stopped until HEMK was complete reacted and the reaction of monoaddition product was completed. Then 1.39 g (12 mmol) of hydroxyethyl acrylate was added, and continued to stir for reaction under heat preservation. A sample was taken for testing every 4 hours of reaction time. The reaction was stopped until the hydroxyethyl acrylate content no longer decreases. The temperature was lowered to 30 C., 6.4 g sodium carbonate aqueous solution with a mass concentration of 5% (3.0 mmol sodium carbonate) was added, and then washed until neutral. The solvent was distilled off under reduced pressure to obtain 4.09 g of the product of formula XVI.

##STR00073##

TABLE-US-00014 TABLE 13 Analysis results of the product of Example 13 by liquid chromatography-mass spectrometry Retention time Value of n.sub.3 Number (min) Content (%) Molecular mass in formula XVI 1 7.29 13.60 873.09 1 2 11.55 21.38 1371.76 2 3 16.04 17.89 1870.43 3 4 17.36 9.96 2369.10 4 5 20.64 15.08 2867.77 5 6 22.42 6.90 3366.44 6 7 23.34 5.46 3865.11 7 8 26.87 4.98 4363.78 8 9 28.91 3.22 4862.45 9 10 32.03 1.51 5361.12 10

Example 14

[0124] This Example provided a photocurable composition, comprising the following components: 4.57 g of Photomer 4072, 4.57 g of Photomer 3316, 0.36 g of the product of Formula IX of Example 1, and 0.5 g of Omnipol TX.

[0125] The method for preparing the above-mentioned photocurable composition comprised the following steps: the above-mentioned components were stirred and dissolved at 60 C., and then cooled to room temperature to prepare a photocurable composition.

Example 15

[0126] This Example provided a photocurable composition, comprising the following components: 4.57 g of Photomer 4072, 4.57 g of Photomer 3316, 0.36 g of the product of Formula XI of Example 4, and 0.5 g of Omnipol TX.

[0127] The method for preparing the above-mentioned photocurable composition comprised the following steps: the above-mentioned components were stirred and dissolved at 60 C., and then cooled to room temperature to prepare a photocurable composition.

Example 16

[0128] This Example provided a photocurable composition, comprising the following components: 4.5 g of Photomer 4072, 4.5 g of Photomer 3316, 0.5 g of the product of Formula XIII of Example 7, and 0.5 g of Omnipol TX.

[0129] The method for preparing the above-mentioned photocurable composition comprised the following steps: the above-mentioned components were stirred and dissolved at 60 C., and then cooled to room temperature to prepare a photocurable composition.

Example 17

[0130] This Example provided a photocurable composition, comprising the following components: 4.5 g of Photomer 4072, 4.5 g of Photomer 3316, 0.5 g of the product of Formula XIV of Example 9, and 0.5 g of Omnipol TX.

[0131] The method for preparing the above-mentioned photocurable composition comprised the following steps: the above-mentioned components were stirred and dissolved at 60 C., and then cooled to room temperature to prepare a photocurable composition.

Example 18

[0132] This Example provided a photocurable composition, comprising the following components: 4.5 g of Photomer 4072, 4.5 g of Photomer 3316, 0.5 g of the product of Formula XV of Example 11, and 0.5 g of Omnipol TX.

[0133] The method for preparing the above-mentioned photocurable composition comprised the following steps: the above-mentioned components were stirred and dissolved at 60 C., and then cooled to room temperature to prepare a photocurable composition.

Comparative Example 1

[0134] This comparative example provided a photocurable composition, comprising the following components: 4.65 g of Photomer 4072, 4.65 g of Photomer 3316, 0.2 g of the Omnirad EMK, and 0.5 g of Omnipol TX.

[0135] The method for preparing the above-mentioned photocurable composition comprised the following steps: the above-mentioned components were stirred and dissolved at 60 C., and then cooled to room temperature to prepare a photocurable composition.

Test Example

[0136] The hardness and curing mobility properties of the photocurable compositions prepared of Examples 14-18 and Comparative Example 1 were tested respectively:

[0137] Pendulum hardness test: a 25 m wire rod was used to cure the above-mentioned photocurable compositions on a coated glass plate (under a 395 nm LED light) at a speed of 10 m/min, and the pendulum hardness after curing was tested.

[0138] Mobility test: a 25 m wire rod was used to cure the above-mentioned photocurable composition on a paper with a coating length and width of 520 cm under a 395 nm LED lamp at a speed of 10 m/min. The 100 cm.sup.2 of cured paper was put into 100 g of acetic acid aqueous solution with a mass content of 3%, then it was placed at 40 C. for 10 days. Then HPLC was used to detect the photoinitiator component (the photoinitiator component refers to the product component of the formula IX of Example 1, the product component of Formula XI of Example 4, the product component of Formula XIII of Example 7, the product component of Formula XIV of Example 9, the product component of Formula XV of Example 11 or the component of Omnirad EMK) that migrates into the acetic acid aqueous solution. The EU model was used for calculation of the results, assuming that 1 kg of food is packaged in a 600 cm.sup.2 printing area, so the results can be converted into g/kg, that is, g of analyte per kg of food (the analyte refers to the product of formula IX of Example 1, the product of formula XI of Example 4, the product of formula XIII of Example 7, the product of formula XIV of Example 9, the product of formula XV of Example 11 or Omnirad EMK). The experimental results of hardness and mobility analysis were shown in Table 14.

TABLE-US-00015 TABLE 14 Example Example Example Example Example Comparative 14 15 16 17 18 Example 1 Pendulum hardness 0.76 0.75 0.75 0.79 0.80 0.77 Mobility (g/kg) 25 23 27 11 6 2180

[0139] It can be seen from the test data that using the bis(dialkylamino)benzophenone compound with an acrylate alkoxy side chain provided by the present application as a co-initiator of the photocurable composition, compared with the commonly used EMK as a co-initiator for photocurable compositions on the market, the hardness of the compounds provided in the present application after curing is similar to that of the control, indicating that they have a similar curing rate. However, because the compound provided by the application has a larger molecular weight and contains polymerizable double bonds, the mobility is significantly reduced. Therefore, the compounds provided in the present application are more suitable for use in food and drug packaging, children's toys and other applications that have strict requirements on substance mobility.

[0140] Obviously, the above examples are merely examples made for clear description, rather limiting the implementations. For those of ordinary skill in the art, other different forms of variations or modifications can also be made on the basis of the above-mentioned description. All embodiments are not necessary to be and cannot be exhaustively listed herein. In addition, obvious variations or modifications derived therefrom all fall within the scope of protection of the present invention.