Amphiphilic polyetherified alpha-keto (hetero)aryl thioester compounds for LED photopolymerization and preparation and use thereof

Abstract

The application discloses an amphiphilic polyetherized alpha-keto(hetero)aryl thioester compound for LED photopolymerization, a preparation method thereof and application thereof. The amphiphilic polyetherized alpha-keto(hetero)aryl thioester compound can be used as an initiator for LED photopolymerization, has good absorption performance in a visible light region above 400 nm, especially shows good initiation performance under a 405 nm LED light source, can effectively initiate photopolymerization of water-based or oil-based photopolymerizable monomers, especially water-based or oil-based (methyl) acrylate monomers, avoids use of a noble metal catalyst, has a simple synthesis route and low synthesis cost, and thus has extremely high practical value.

Description

Technical Field

[0001] This invention belongs to the field of photopolymerization technology and relates to amphiphilic polyetherified α-keto(hetero)aryl thioester compounds. These compounds can be used as photoinitiators, especially suitable for LED photopolymerization. This invention also relates to the preparation and application of amphiphilic polyetherified α-keto(hetero)aryl thioester compounds. Background Technology

[0002] With the continuous development of LED photopolymerization technology, it is necessary to develop photoinitiators suitable for LED light sources to meet the widespread application requirements of LED photopolymerization. Some such photoinitiators already exist in the existing technology; for example, CN104817653A discloses a coumarin aldehyde oxime ester compound suitable for UV-LED curing, and CN102492059A discloses a substituted diphenyl sulfide ketone oxime ester photoinitiator. However, the reported LED photoinitiators currently available typically contain highly conjugated groups in their molecular structures, making the synthesis of such photoinitiators complex and causing inconvenience for practical production applications.

[0003] In addition, waterborne photoinitiator systems, which have many advantages such as low toxicity, environmental friendliness, and safety, have become one of the research hotspots in the field of photopolymerization in recent years due to their unique properties. However, most waterborne photoinitiator molecules are currently salts containing metal ions, and the introduction of metal ions can cause certain harm to the performance of photocurable materials.

[0004] In light of this, researching and developing novel amphiphilic photoinitiators with simple structures and synthetic routes for use in LED light sources remains one of the core tasks in this field. Furthermore, photopolymers, especially poly(meth)acrylates, are widely used in biomedical materials and other fields due to their excellent mechanical properties, good reprocessability, and weather resistance. Therefore, developing amphiphilic photoinitiators that can effectively polymerize waterborne or oil-based photopolymerizable monomers, especially waterborne or oil-based (meth)acrylate monomers, is also urgently needed in the field of photopolymerization. Summary of the Invention

[0005] To promote the development of LED photopolymerization technology, the inventors have been committed to the research and application of LED photopolymerization technology, especially the continuous research and development of more photoinitiators suitable for LED photopolymerization light sources. In particular, given the problems existing in the current technology, the inventors have conducted extensive and in-depth research on photoinitiators suitable for LED photopolymerization, aiming to find a novel, highly efficient, amphiphilic photoinitiator that can effectively initiate the photopolymerization reaction of water-based or oil-based photopolymerizable monomers, especially water-based or oil-based (meth)acrylate monomers, while avoiding the use of expensive metal catalysts and having a simple synthetic route.

[0006] The inventors have surprisingly discovered that by simultaneously introducing α-carbonyl ketones and aryl or heteroaryl thioester groups into a single molecule and then polyetherifying it, a novel class of highly efficient polyetherified α-ketone (hetero)aryl thioester LED photoinitiators can be synthesized. The prepared initiator exhibits excellent absorption performance in the visible light region above 400 nm, which can be well matched with the wavelength of LED light sources. In particular, the photoinitiator of this invention demonstrates excellent initiation performance under an LED light source at 405 nm, effectively initiating the photopolymerization reaction of aqueous or oil-based photopolymerizable monomers, especially aqueous or oil-based (meth)acrylate monomers. This avoids the use of expensive metal catalysts and features a simple synthesis route and low synthesis cost, thus possessing extremely high practical value.

[0007] The objective of this invention is achieved based on the aforementioned findings.

[0008] Therefore, one object of the present invention is to provide an amphiphilic polyetherified α-ketone(hetero)aryl thioester compound whose absorption wavelength is not only suitable for LED light source polymerization, but also can effectively initiate the photopolymerization reaction of aqueous or oily (meth)acrylate monomers, and the synthesis route is simple, while avoiding the use of precious metal catalysts.

[0009] Another object of the present invention is to provide a method for preparing the amphiphilic polyetherified α-ketone(hetero)aryl thioester compounds of the present invention.

[0010] Another object of the present invention is to provide the use of the amphiphilic polyetherified α-ketone(hetero)aryl thioester compounds of the present invention as photoinitiators in LED photopolymerization.

[0011] The technical solution for achieving the above-mentioned objectives of this invention can be summarized as follows:

[0012] 1. An amphiphilic polyetherified α-keto(hetero)aryl thioester compound of general formula (I):

[0013]

[0014] in:

[0015] M indicates C6-C 18 aryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S, and O, wherein C6-C 18 The aryl group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S, and O may optionally be substituted by one or more groups independently selected from the group consisting of halogens, hydroxyl groups, etc.

[0016] -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkyl alkylthio, C4-C 20 Alkyl cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy group, C6-C 18 Arylthio, C7-C 20 Aryl group, C7-C 20 Arylalkyloxy, C7-C 20 Aryl alkyl thio group, C7-C 20 Alkyl, C7-C 20 Alkyloxy group, C7-C 20 Alkyl aryl thioyl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S, and O, wherein the mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkyl alkylthio, C4-C 20 Alkyl cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy group, C6-C 18 Arylthio, C7-C 20 Aryl group, C7-C 20 Arylalkyloxy, C7-C 20 Aryl alkyl thio group, C7-C 20 Alkyl, C7-C 20 Alkyloxy group, C7-C 20 The alkylarylthio group or the 5-18-membered heteroaryl group containing one or more heteroatoms selected from N, S and O may optionally be substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, carboxylic acid ester or amino.

[0017] L indicates

[0018] Where R 15 It is H or C1-C4 alkyl, preferably methyl;

[0019] n is between 0 and 10, preferably an integer between 0 and 4.

[0020] m is a number between 1 and 4, preferably an integer between 1 and 2.

[0021] 2. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to item 1, wherein: M represents C6-C 18 Aryl or 5-18 membered heteroaryl groups containing one or more heteroatoms selected from N, S, and O.

[0022] C6-C 18 The aryl group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S, and O may optionally be substituted by one or more groups independently selected from the group consisting of halogens, hydroxyl groups, etc.

[0023] -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 cycloalkyl alkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy group, C6-C 18 Arylthio, C7-C 20 Aryl group, C7-C 20 Arylalkyloxy, C7-C 20 Aryl sulfide or C7-C 20 Alkyl aryl; wherein mono(C1-C6)amino, di(C1-C6)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 cycloalkyl alkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy group, C6-C 18 Arylthio, C7-C 20 Aryl group, C7-C 20 Arylalkyloxy, C7-C 20 Aryl sulfide or C7-C 20The alkylaryl group may optionally be substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, carboxylic acid ester, or amino groups;

[0024] More preferably, C6-C 18 The aryl group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S, and O may optionally be substituted by one or more groups independently selected from the group consisting of: halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 cycloalkyl alkylthio, C6-C 18 Aryl, C6-C 18 aryloxy or C6-C 18 Arylthioyl groups; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 cycloalkyl alkylthio, C6-C 18 Aryl, C6-C 18 aryloxy or C6-C 18 The aryl thio group may optionally be substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, carboxylic acid ester, or amino groups.

[0025] More preferably, C6-C 18 The aryl group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S, and O may optionally be substituted by one or more groups independently selected from the group consisting of: halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Halogenated alkoxy groups, C1-C 20 Alkylthio, C1-C 20Haloalkylthio group, C3-C 10 cycloalkyl, C6-C 18 Aryl, C6-C 18 aryloxy or C6-C 18 Aryl thiols; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C3-C 10 cycloalkyl, C6-C 18 Aryl, C6-C 18 aryloxy groups and C6-C 18 The aryl thio group may optionally be substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, carboxylic acid ester, or amino groups.

[0026] More preferably, C6-C 18 The aryl group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S, and O may optionally be substituted by one or more groups independently selected from the group consisting of: halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, C1-C 20 Alkyl, C1-C 20 Alkyl group, -CF3, -OCF3 or -OC6H5.

[0027] 3. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to claim 1 or 2, wherein:

[0028] M indicates C6-C 18 Aryl or 5-18 membered heteroaryl groups containing one or more heteroatoms selected from N, S, and O.

[0029] C6-C 18 The aryl group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may optionally be substituted with methyl or methoxy groups.

[0030] 4. An amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to any one of items 1-3, wherein:

[0031] M represents

[0032] R1 is selected from O, S, or -NR. 10 -;

[0033] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl group, and -NO2, respectively.

[0034] -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkyl alkylthio, C4-C 20 Alkyl cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy group, C6-C 18 Arylthio, C7-C 20 Aryl group, C7-C 20 Arylalkyloxy, C7-C 20 Aryl alkyl thio group, C7-C 20 Alkyl, C7-C 20 Alkyloxy group, C7-C 20 Alkyl aryl thioyl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S, and O; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkyl alkylthio, C4-C 20 Alkyl cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy group, C6-C 18 Arylthio, C7-C 20 Aryl group, C7-C 20 Arylalkyloxy, C7-C 20 Aryl alkyl thio group, C7-C 20 Alkyl, C7-C 20 Alkyloxy group, C7-C 20 The alkylarylthio group or the 5-18-membered heteroaryl group containing one or more heteroatoms selected from N, S and O may optionally be substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, carboxylic acid ester or amino.

[0035] R 10 Indicates hydrogen, C1-C 20 Alkyl, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Alkyl cycloalkyl, C6-C 18Aryl, C7-C 20 Aryl group, C7-C 20 Alkyl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S, and O; wherein C1-C 20 Alkyl, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Alkyl cycloalkyl, C6-C 18 Aryl, C7-C 20 Aryl group, C7-C 20 An alkylaryl group or a 5-18-membered heteroaryl group containing one or more heteroatoms selected from N, S, and O may optionally be substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, carboxylic acid ester, or amino groups.

[0036] 5. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to item 4, wherein M represents R2, R3, R4, R5, R6, R7, R8, and R9 are defined as in item 4.

[0037] 6. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to claim 4 or 5, wherein:

[0038] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl group, and -NO2, respectively.

[0039] -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 cycloalkyl alkylthio, C6-C 18 Aryl, C6-C 18 aryloxy or C6-C 18 Arylthioyl groups; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20cycloalkyl alkylthio, C6-C 18 Aryl, C6-C 18 aryloxy or C6-C 18 The aryl thio group may optionally be substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, carboxylic acid ester, or amino groups.

[0040] More preferably,

[0041] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl group, and -NO2, respectively.

[0042] -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Halogenated alkoxy groups, C1-C 20 Alkylthio, C1-C 20 Haloalkylthio group, C3-C 10 cycloalkyl, C6-C 18 Aryl, C6-C 18 aryloxy or C6-C 18 Aryl thiols; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C3-C 10 cycloalkyl, C6-C 18 Aryl, C6-C 18 aryloxy groups and C6-C 18 The aryl thio group may optionally be substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, carboxylic acid ester, or amino groups.

[0043] More preferably,

[0044] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl group, and -NO2, respectively.

[0045] -CN, -COOH, -CHO, amino, C1-C 20 Alkyl, C1-C 20 Alkyl, -CF3, -OCF3 or -OC6H5;

[0046] Most preferably,

[0047] R2, R3, R5, R6, R7, R8, and R9 are the same and are H; R4 is methyl or methoxy.

[0048] 7. An amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to any one of items 1-6, wherein:

[0049] R 10 Indicates hydrogen, C1-C 20 Alkyl, C6-C 18 Aryl, C7-C 20 Aryl group, C7-C 20 Alkyl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S, and O; wherein C1-C 20 Alkyl, C6-C 18 Aryl, C7-C 20 Aryl group, C7-C 20 An alkylaryl group or a 5-18-membered heteroaryl group containing one or more heteroatoms selected from N, S, and O may optionally be substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, carboxylic acid ester, or amino groups.

[0050] 8. An amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to any one of claims 1-7, wherein:

[0051] R 15 It is methyl;

[0052] n is 2;

[0053] m is 1.

[0054] 9. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to any one of items 1-8, wherein:

[0055]

[0056] 10. A method for preparing amphiphilic polyetherified α-keto(hetero)aryl thioester compounds according to any one of claims 1-9, comprising:

[0057] (a) make and The reaction yields an intermediate product. as well as

[0058] (b) make and The reaction, thereby obtaining

[0059]

[0060] Where M, m, n and R 15 As defined in any of items 1-9.

[0061] 11. The method according to item 10, wherein the molar ratio of M-SH to oxalyl chloride is 1:1.1-1:2, preferably 1:1.2-1:2, more preferably 1:1.2-1:1.8.

[0062] 12. The method according to item 10 or 11, wherein the molar ratio of intermediate product (A) to raw material (C) is 1:1.1-1:3, preferably 1:1.1-1:2, more preferably 1:1.2-1:2.

[0063] 13. The method according to any one of items 10-12, wherein the reaction in step (b) is carried out in the presence of one or more catalysts selected from the group consisting of 4-dimethylaminopyridine, piperidine, 3-methylpiperidine and triethylamine, preferably 4-dimethylaminopyridine; and / or the molar amount of the catalyst is 1-10% of the intermediate product (A), preferably 5-10%.

[0064] 14. The method according to any one of items 10-13, wherein the reaction in step (b) is carried out in the presence of one or more dehydrating agents selected from the group consisting of: dicyclohexylcarbodiimide, diisopropylcarbodiimide, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, preferably dicyclohexylcarbodiimide; and / or the molar amount of the dehydrating agent is 100-150% of the intermediate product (A), preferably 120-140%.

[0065] 15. A photopolymerizable composition comprising:

[0066] (A) At least one monomer or oligoolefin is an unsaturated photopolymerizable compound, and

[0067] (B) At least one amphiphilic polyetherified α-ketone(hetero)aryl thioester compound obtained by any one of the methods in items 1-9 or according to any one of the methods in items 10-14.

[0068] 16. Use of amphiphilic polyetherified α-keto(hetero)aryl thioester compounds obtained by any of the methods in items 1-9 or according to any of the methods in items 10-14 as photoinitiators in photopolymerization.

[0069] 17. Use of amphiphilic polyetherified α-keto(hetero)aryl thioester compounds obtained by any of the methods in items 1-9 or according to any of the methods in items 10-14 in the preparation of biopolymer materials. Attached Figure Description

[0070] Figure 1 This is a diagram illustrating the initiation mechanism of the photoinitiator provided by this invention;

[0071] Figure 2 This is the UV-Vis absorption spectrum of the photoinitiator MO-TGTE in Example 2;

[0072] Figure 3 This is a photopolymerization kinetic diagram of the photoinitiator MO-TGTE in Example 2, which initiates the polymerization of oily monomers tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), and watery monomers polyethylene glycol (400) diacrylate (PEG(400)DA) under a 405nm LED light source. Detailed Implementation

[0073] The first aspect of the present invention provides an amphiphilic polyetherified α-keto(hetero)aryl thioester compound of general formula (I):

[0074]

[0075] in:

[0076] M indicates C6-C 18 aryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S, and O, wherein C6-C 18 The aryl group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S, and O may optionally be substituted by one or more groups independently selected from the group consisting of halogens, hydroxyl groups, etc.

[0077] -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkyl alkylthio, C4-C 20 Alkyl cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy group, C6-C 18 Arylthio, C7-C 20 Aryl group, C7-C 20 Arylalkyloxy, C7-C 20 Aryl alkyl thio group, C7-C 20 Alkyl, C7-C 20 Alkyloxy group, C7-C 20 Alkyl aryl thioyl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S, and O, wherein the mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkyl alkylthio, C4-C 20 Alkyl cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy group, C6-C 18 Arylthio, C7-C 20 Aryl group, C7-C 20 Arylalkyloxy, C7-C 20 Aryl alkyl thio group, C7-C 20 Alkyl, C7-C 20 Alkyloxy group, C7-C 20 The alkylarylthio group or the 5-18-membered heteroaryl group containing one or more heteroatoms selected from N, S and O may optionally be substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, carboxylic acid ester or amino.

[0078] L indicates

[0079] Where R 15 It is H or C1-C4 alkyl, preferably methyl;

[0080] n is between 0 and 10, preferably an integer between 0 and 4.

[0081] m is a number between 1 and 4, preferably an integer between 1 and 2.

[0082] In this invention, the prefix "C" n -C m "In each case, it indicates that the number of carbon atoms contained in the group is n to m."

[0083] "Halogen" refers to fluorine, chlorine, bromine, and iodine, and combinations thereof. In this invention, preferred halogens include F, Cl, or combinations thereof.

[0084] The term "C" used in this article n -C m"Alkyl" refers to a saturated hydrocarbon group having n to m carbon atoms, for example 1-20, preferably 1-12, more preferably 1-8, particularly preferably 1-6, and especially preferably 1-4 carbon atoms, which may be branched or unbranched. Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their isomers, especially methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1 3-Dimethylbutyl, 2,2-Dimethylbutyl, 2,3-Dimethylbutyl, 3,3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1,1,2-Trimethylpropyl, 1,2,2-Trimethylpropyl, 1-Ethyl-1-Methylpropyl, 1-Ethyl-2-Methylpropyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl, n-Undecyl, n-Dodecyl and their isomers, etc. C1- C6 alkyl groups can be methyl, ethyl, propyl, butyl, pentyl, hexyl, and their isomers, especially methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, etc. C1-C4 alkyl groups can be methyl, ethyl, propyl, butyl, and their isomers, especially methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc.

[0085] The term "C3-C" is used in this article. m "Cycloalkyl" refers to a saturated alicyclic monocyclic group having 3 to m, for example 3-10, preferably 3-8, and more preferably 5-6 cyclic carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl.

[0086] The term "C4-C" m "Cycloalkyl" means an alkyl group substituted with a cycloalkyl group and containing a total of 4 to m carbon atoms, for example 4-20 carbon atoms, preferably 4-12, more preferably 4-10, and most preferably 4-8 carbon atoms. Alkyl and cycloalkyl are used as defined herein, and examples include cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclobutylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl, etc.

[0087] The term "C4-C" m"alkylcycloalkyl" means a cycloalkyl group substituted with an alkyl group and containing a total of 4 to m carbon atoms, for example 4-20 carbon atoms, preferably 4-12, more preferably 4-10, and most preferably 4-8 carbon atoms. Alkyl and cycloalkyl are used as defined herein, and examples include methylcyclopropyl, ethylcyclopropyl, propylcyclopropyl, butylcyclopropyl, methylcyclobutyl, ethylcyclobutyl, propylcyclobutyl, butylcyclobutyl, methylcyclopentyl, ethylcyclopentyl, propylcyclopentyl, butylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexyl, etc.

[0088] The term "C6-C" is used in this article. m "Aryl" refers to a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon group containing 6 to m carbon atoms, for example 6-18, preferably 6-10 carbon atoms. As a C6-C... m Examples of aryl groups include phenyl, azulel, cycloheptatrienyl, biphenyl, dicyclopentadienylphenyl, fluorenyl, phenanthrene, terphenyl, pyrene, and tetraphenyl. It contains alkyl, anthracene, indole, cyclopentadienyl, and naphthyl.

[0089] "A 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S, and O" is understood to refer to a group having 5-18 ring members, such as 5-16, 5-14, 5-10, or 5-8, or 8-14, 9-14, or 9-13 ring members, wherein at least one ring atom is a heteroatom selected from N, O, and S, more preferably N. The heteroaryl group preferably has 1-3, for example, 1 or 2 heteroatoms. More preferably, the heteroaryl group is a ring system having two or three fused rings, having 8-14, 9-14, or 9-13 ring members. Examples of heteroaryl groups include thiophene, benzo[b]thiophene, naphtho[2,3-b]thiophene, thianthyl, furanyl, dibenzofuranyl, benzofuranyl, chromenyl, xanthyl, thioxanyl, pyrrolyl, imidazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indoleyl, isoindolyl, indolyl, indazoleyl, purinyl, quinazinyl, isoquinolinyl, quinolinyl, phthalazinyl, naphthidyl, quinoxalinyl, quinazolinyl, cyclophosphinyl, pteridinyl, carbazolyl, phenanthridine, acridineyl, naphthalene-intercalated diazoxide-phenyl, phenanthrololinyl, phenazinyl, isothiazolyl, phenothiazinyl, isothiazolyl, phenanthiazinyl, and so on. azole, furazolidone, phen Azinyl, 7-phenanthrene, anthraquinone-2-yl (=9,10-dioxo-9,10-dihydroanthracene-2-yl), 3-benzo[b]thiophene, 5-benzo[b]thiophene, 2-benzo[b]thiophene, 4-dibenzofuranyl, 4-7-dibenzofuranyl, 4-methyl-7-dibenzofuranyl, 2-xanthonyl, 8-methyl-2-xanthonyl, 3-xanthonyl, phenanthrene Thiyl, 2,7-phen Thioyl, 2-pyrrolith, 3-pyrrolith, 5-methyl-3-pyrrolith, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl, 2-ethyl-4-imidazolyl, 2-ethyl-5-imidazolyl, 1H-tetrazole-5-yl, 3-pyrazolyl, 1-methyl-3-pyrazolyl, 1-propyl-4-pyrazolyl, 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl, 2-indoleyl, 2-methyl-3-isoindolyl, 2-methyl-1-isoindolyl, 1-methyl-2-indolyl 1-Methyl-3-indolyl, 1,5-dimethyl-2-indolyl, 1-methyl-3-indazolyl, 2,7-dimethyl-8-purinyl, 2-methoxy-7-methyl-8-purinyl, 2-quinazinyl, 3-isoquinolinyl, 6-isoquinolinyl, 7-isoquinolinyl, 3-methoxy-6-isoquinolinyl, 2-quinolinyl, 6-quinolinyl, 7-quinolinyl, 2-methoxy-3-quinolinyl, 2-methoxy-6-quinolinyl, 6-phthalazinyl, 7-phthalazinyl, 1-methoxy-6-phthalazinyl, 1, 4-Dimethoxy-6-phthalazinyl, 1,8-naphthid-2-yl, 2-quinoxalinyl, 6-quinoxalinyl, 2,3-dimethyl-6-quinoxalinyl, 2,3-dimethoxy-6-quinoxalinyl, 2-quinoxalinyl, 7-quinoxalinyl, 2-dimethylamino-6-quinoxalinyl, 3-terpinenyl, 6-terpinenyl, 7-terpinenyl, 3-methoxy-7-terpinenyl, 2-pteridyl, 6-pteridyl, 7-pteridyl, 6,7-dimethoxy-2-pteridyl, 2-carbazole, 3-carbazole, 9-methyl 2-Carbazolyl, 9-Methyl-3-Carbazolyl, β-Carblin-3-yl, 1-Methyl-β-Carblin-3-yl, 1-Methyl-β-Carblin-6-yl, 3-Phenyridyl, 2-Acridineyl, 3-Acridineyl, 2-Naphthalene-2-diazoxide, 1-Methyl-5-Naphthalene-2-diazoxide, 5-Phenyrrolinyl, 6-Phenyrrolinyl, 1-Phenazinyl, 2-Phenazinyl, 3-Isothiazolyl, 4-Isothiazolyl, 5-Isothiazolyl, 2-Phenthiazolyl, 3-Phenthiazolyl, 10-Methyl-3-Phenthiazolyl, 3-Iso-2-Carbazolyl azole group, 4-iso azole group, 5-iso azole, 4-methyl-3-furazanyl, 2-phen Azine, 10-methyl-2-phen Azine group, etc.

[0090] The term "C7-C" m "Aryl" means an alkyl group substituted with an aryl group and containing a total of 7 to m carbon atoms, for example 7-20 carbon atoms, preferably 7-12 carbon atoms. Alkyl and aryl are used as defined herein, and examples include benzyl, phenethyl, naphthylmethyl, naphthylethyl, etc.

[0091] The term "C7-C" m"Alkylaryl" means an aryl group substituted with an alkyl group and containing a total of 7 to m carbon atoms, such as 7-20 carbon atoms, preferably 7-12 carbon atoms. Alkyl and aryl are as defined herein, and examples include methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, methylnaphthyl, ethylnaphthyl, etc.

[0092] Term "C" n -C m "Alkoxy" refers to the compound formed by the carbon atom in C2O2. n -C m alkyl corresponding to open chain C n -C m In alkanes, an oxygen atom is bonded to any carbon atom as a linking group. n -C m Alkyl groups, such as C1-C 20 Alkoxy, preferably C1-C 12 Alkoxy groups, more preferably C1-C8 alkoxy groups, and particularly preferably C1-C6 alkoxy groups. Examples include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, and their isomers, especially methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy, and their isomers. C1-C4 alkoxy groups can be methoxy, ethoxy, propoxy, butoxy, and their isomers, especially methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, etc.

[0093] The term "C4-C" m "Cycloalkylalkoxy" refers to an alkoxy group substituted with a cycloalkyl group and containing a total of 4 to m carbon atoms, for example 4 to 20, preferably 4 to 12 carbon atoms, and more preferably 4 to 10 carbon atoms. The cycloalkyl group is as defined herein. Examples include cyclopropylmethoxy, cyclopropylethoxy, cyclopropylpropoxy, cyclopropylbutoxy, cyclobutylmethoxy, cyclobutylethoxy, cyclobutylpropoxy, cyclobutylbutoxy, cyclopentylmethoxy, cyclopentylethoxy, cyclopentylpropoxy, cyclopentylbutoxy, cyclohexylmethoxy, cyclohexylethoxy, cyclohexylpropoxy, cyclohexylbutoxy, etc.

[0094] The term "C6-C" is used in this article. m "Aryloxy group" refers to the group formed at C6-C6. m C6-C corresponding to aryl m Any aromatic carbon atom in an aromatic hydrocarbon has an oxygen atom bonded to it as a linking group (C6-C). m Aryl groups, such as phenoxy, toluoxy, naphthoxy, etc.

[0095] The term "C7-C" is used in this article. m "Arylalkyloxy" refers to the alkyl group formed at C7-C6.m Aryl groups have an oxygen atom bonded to the alkyl carbon atom as a linking group at the C7-C. m Aryl groups, such as benzyloxy, phenylethoxy, naphthoxy, naphthoxy, etc.

[0096] The term "C7-C" m "alkylaryloxy" refers to the alkylaryloxy group at C7-C6. m The aryl group corresponds to a C7-C structure with an oxygen atom bonded to the aryl carbon atom as a linking group. m Alkyl groups, examples of which include methylphenoxy, dimethylphenoxy, trimethylphenoxy, ethylphenoxy, diethylphenoxy, triethylphenoxy, methylnaphthoxy, ethylnaphthoxy, etc.

[0097] Term "C" n -C m "Alkylthio" refers to the group with a C-position of 10 ... n -C m alkyl corresponding to open chain C n -C m In alkanes, a sulfur atom is bonded to any carbon atom as a linking group. n -C m Alkyl groups, such as C1-C 20 Alkylthio group, preferably C1-C 12 Alkylthio, more preferably C1-C8 alkylthio, and particularly preferably C1-C6 alkylthio. Examples include methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio, tert-butylthio, pentylthio, isopentylthio, hexylthio, heptylthio, octylthio, isooctylthio, and their isomers. C1-C4 alkylthio can be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio, tert-butylthio, etc.

[0098] The term "C4-C" m "Cycloalkyl alkylthio" refers to an alkylthio group substituted with a cycloalkyl group and containing a total of 4 to m carbon atoms, for example, 4 to 20, preferably 4 to 12 carbon atoms, and more preferably 4 to 10 carbon atoms. The cycloalkyl and alkylthio groups are as defined herein. Examples include cyclopropylmethylthio, cyclopropylethylthio, cyclopropylpropylthio, cyclopropylbutylthio, cyclobutylmethylthio, cyclobutylethylthio, cyclobutylpropylthio, cyclobutylbutylthio, cyclopentylmethylthio, cyclopentylethylthio, cyclopentylpropylthio, cyclopentylbutylthio, cyclohexylmethylthio, cyclohexylethylthio, cyclohexylpropylthio, cyclohexylbutylthio, etc.

[0099] The term "C6-C" is used in this article. m "Arylthio" refers to the group formed at C6-C6. m C6-C corresponding to aryl mAny C6-C aromatic hydrocarbon with a sulfur atom bonded to a carbon atom as a linking group m Aryl groups, such as phenylthio, toluenethio, naphthio, etc.

[0100] The term "C7-C" is used in this article. m "Aryl thio" refers to the group formed at C7-C6. m The alkyl group corresponding to an alkyl carbon atom has a sulfur atom bonded to it as a linking group at C7-C. m Aryl groups, such as phenylthio, phenylethylthio, naphthiomethylthio, naphthylethylthio, etc.

[0101] The term "C7-C" m "alkylarylthio" refers to the group formed at C7-C6. m The aryl group corresponds to a C7-C structure in which a sulfur atom is bonded to the aryl carbon atom as a linking group. m Alkyl groups, examples of which include methylphenylthio, dimethylphenylthio, trimethylphenylthio, ethylphenylthio, diethylphenylthio, triethylphenylthio, methylnaphthio, ethylnaphthio, etc.

[0102] “C1-C 20 "Halogenated alkyl" includes C1-C 12 Haloalkyl, C1-C8 haloalkyl, C1-C6 haloalkyl, C1-C4 haloalkyl. The halogen and alkyl groups in haloalkyl are as defined herein.

[0103] “C1-C 20 "Haloalkoxy" includes C1-C 12 Halogenated alkoxy groups, C1-C8 halogenated alkoxy groups, C1-C6 halogenated alkoxy groups, and C1-C4 halogenated alkoxy groups. The halogen and alkoxy groups in halogenated alkoxy groups are as defined herein.

[0104] “C1-C 20 "Haloalkylthio" includes C1-C 12 Haloalkylthio groups, C1-C8 haloalkylthio groups, C1-C6 haloalkylthio groups, and C1-C4 haloalkylthio groups. The halogen and alkylthio groups in haloalkylthio groups are as defined in this document for halogens and alkoxy groups.

[0105] In a preferred embodiment of the present invention

[0106] M indicates C6-C 18 Aryl or 5-18 membered heteroaryl groups containing one or more heteroatoms selected from N, S, and O.

[0107] C6-C 18The aryl group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S, and O may optionally be substituted by one or more groups independently selected from the group consisting of halogens, hydroxyl groups, etc.

[0108] -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 cycloalkyl alkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy group, C6-C 18 Arylthio, C7-C 20 Aryl group, C7-C 20 Arylalkyloxy, C7-C 20 Aryl sulfide or C7-C 20 Alkyl aryl; wherein mono(C1-C6)amino, di(C1-C6)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 cycloalkyl alkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy group, C6-C 18 Arylthio, C7-C 20 Aryl group, C7-C 20 Arylalkyloxy, C7-C 20 Aryl sulfide or C7-C 20 The alkylaryl group may optionally be substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, carboxylic acid ester, or amino groups;

[0109] More preferably, C6-C 18 The aryl group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S, and O may optionally be substituted by one or more groups independently selected from the group consisting of: halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 cycloalkyl alkylthio, C6-C 18 Aryl, C6-C 18 aryloxy or C6-C 18 Arylthioyl groups; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 cycloalkyl alkylthio, C6-C 18 Aryl, C6-C 18 aryloxy or C6-C 18 The aryl thio group may optionally be substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, carboxylic acid ester, or amino groups.

[0110] More preferably, C6-C 18 The aryl group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S, and O may optionally be substituted by one or more groups independently selected from the group consisting of:

[0111] Halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Halogenated alkoxy groups, C1-C 20 Alkylthio, C1-C 20 Haloalkylthio group, C3-C 10 cycloalkyl, C6-C 18 Aryl, C6-C 18 aryloxy or C6-C 18 Aryl thiols; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C3-C 10 cycloalkyl, C6-C 18 Aryl, C6-C 18 aryloxy groups and C6-C 18The aryl thio group may optionally be substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, carboxylic acid ester, or amino groups.

[0112] More preferably, C6-C 18 The aryl group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S, and O may optionally be substituted by one or more groups independently selected from the group consisting of: halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, C1-C 20 Alkyl, C1-C 20 Alkyl, -CF3, -OCF3 or -OC6H5;

[0113] Most preferably, C6-C 18 The aryl group or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may optionally be substituted with methyl or methoxy groups.

[0114] In a preferred embodiment of the present invention

[0115] M represents

[0116] R1 is selected from O, S, or -NR. 10 -;

[0117] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl group, and -NO2, respectively.

[0118] -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkyl alkylthio, C4-C 20 Alkyl cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy group, C6-C 18 Arylthio, C7-C 20 Aryl group, C7-C 20 Arylalkyloxy, C7-C 20 Aryl alkyl thio group, C7-C 20 Alkyl, C7-C 20 Alkyloxy group, C7-C 20Alkyl aryl thioyl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S, and O; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkyl alkylthio, C4-C 20 Alkyl cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy group, C6-C 18 Arylthio, C7-C 20 Aryl group, C7-C 20 Arylalkyloxy, C7-C 20 Aryl alkyl thio group, C7-C 20 Alkyl, C7-C 20 Alkyloxy group, C7-C 20 The alkylarylthio group or the 5-18-membered heteroaryl group containing one or more heteroatoms selected from N, S and O may optionally be substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, carboxylic acid ester or amino.

[0119] R 10 Indicates hydrogen, C1-C 20 Alkyl, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Alkyl cycloalkyl, C6-C 18 Aryl, C7-C 20 Aryl group, C7-C 20 Alkyl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S, and O; wherein C1-C 20 Alkyl, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Alkyl cycloalkyl, C6-C 18 Aryl, C7-C 20 Aryl group, C7-C 20 An alkylaryl group or a 5-18-membered heteroaryl group containing one or more heteroatoms selected from N, S, and O may optionally be substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, carboxylic acid ester, or amino groups.

[0120] In a preferred embodiment of the present invention

[0121] M represents in:

[0122] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl group, and -NO2, respectively.

[0123] -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkyl alkylthio, C4-C 20 Alkyl cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy group, C6-C 18 Arylthio, C7-C 20 Aryl group, C7-C 20 Arylalkyloxy, C7-C 20 Aryl alkyl thio group, C7-C 20 Alkyl, C7-C 20 Alkyloxy group, C7-C 20 Alkyl aryl thioyl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S, and O; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkyl alkylthio, C4-C 20 Alkyl cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy group, C6-C 18 Arylthio, C7-C 20 Aryl group, C7-C 20 Arylalkyloxy, C7-C 20 Aryl alkyl thio group, C7-C 20 Alkyl, C7-C 20 Alkyloxy group, C7-C 20The alkylarylthio group or the 5-18-membered heteroaryl group containing one or more heteroatoms selected from N, S and O may optionally be substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, carboxylic acid ester or amino.

[0124] In a more preferred embodiment of the present invention

[0125] M represents in:

[0126] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl group, and -NO2, respectively.

[0127] -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 cycloalkyl alkylthio, C6-C 18 Aryl, C6-C 18 aryloxy or C6-C 18 Arylthioyl groups; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C3-C 10 cycloalkyl, C4-C 20 cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 cycloalkyl alkylthio, C6-C 18 Aryl, C6-C 18 aryloxy or C6-C 18 The aryl thio group may optionally be substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, carboxylic acid ester, or amino groups; more preferably,

[0128] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl group, and -NO2, respectively.

[0129] -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Halogenated alkoxy groups, C1-C 20 Alkylthio, C1-C 20 Haloalkylthio group, C3-C 10 cycloalkyl, C6-C 18 Aryl, C6-C 18 aryloxy or C6-C 18 Aryl thiols; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C3-C 10 cycloalkyl, C6-C 18 Aryl, C6-C 18 aryloxy groups and C6-C 18 The aryl thio group may optionally be substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, carboxylic acid ester, or amino groups.

[0130] More preferably,

[0131] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl group, and -NO2, respectively.

[0132] -CN, -COOH, -CHO, amino, C1-C 20 Alkyl, C1-C 20 Alkyl, -CF3, -OCF3 or -OC6H5;

[0133] Most preferably,

[0134] R2, R3, R5, R6, R7, R8, and R9 are the same and are H; R4 is methyl or methoxy.

[0135] In a preferred embodiment of the present invention

[0136] R 10 Indicates hydrogen, C1-C 20 Alkyl, C6-C 18 Aryl, C7-C 20 Aryl group, C7-C 20 Alkyl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S, and O; wherein C1-C 20 Alkyl, C6-C 18 Aryl, C7-C 20 Aryl group, C7-C 20 An alkylaryl group or a 5-18-membered heteroaryl group containing one or more heteroatoms selected from N, S, and O may optionally be substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, mercapto, carboxyl, sulfonic acid, carboxylic acid ester, or amino groups.

[0137] In a preferred embodiment of the present invention, M is... R2, R3, R5, and R6 are the same and are H; R4 is methyl or methoxy.

[0138] In yet another preferred embodiment of the present invention, M is... R2, R3, R5, R6, R7, R8, and R9 are the same and are H.

[0139] In a particularly preferred embodiment of the invention, R 15 It is a methyl group; n is 2; m is 1.

[0140] As a specific example of amphiphilic polyetherified α-keto(hetero)aryl thioester compounds of general formula (I), one can mention

[0141] A second aspect of the present invention relates to a method for preparing amphiphilic polyetherified α-ketone(hetero)aryl thioester compounds of general formula (I) of the present invention, comprising:

[0142] (a) make and The reaction yields an intermediate product. as well as

[0143] (b) make and The reaction, thereby obtaining

[0144]

[0145] Where M, m, n and R 15 As defined above.

[0146] In step (a) of the method of the present invention, the molar ratio of M-SH to oxaloyl chloride is 1:1.1-1:2, preferably 1:1.2-1:2, and more preferably 1:1.2-1:1.8.

[0147] Step (a) of the method of the present invention is typically carried out in a solvent, preferably an organic solvent. There are no particular limitations on the type of solvent, as long as it can dissolve the reactants and is chemically inert to the reaction, i.e., does not participate in the reaction. Examples of commonly used solvents include dichloromethane, ethyl acetate, tetrahydrofuran, and N,N-dimethylformamide. Preferably, the reaction in step (a) is carried out in tetrahydrofuran.

[0148] More specifically, in step (a) of the method of the present invention, M-SH is dissolved in an appropriate amount of solvent and added to a reaction vessel. Then, oxalyl chloride is dissolved in the same solvent and transferred to a dropping funnel, which is then added dropwise to the reaction vessel. The reaction is stirred at -10 to 20°C, preferably in an ice-water bath, for 2-12 hours, more preferably 4-10 hours. Subsequently, an appropriate amount of deionized water is added to the reaction system, and the mixture is stirred vigorously for 0.5-4 hours, more preferably 1-3 hours. After the reaction is completed, the aqueous phase is separated, and the solvent is removed by vacuum distillation to obtain the crude product. The intermediate product (A) is obtained by silica gel column chromatography.

[0149] Step (b) of the method of the present invention is carried out in a solvent in the presence of a dehydrating agent and a catalyst. Suitable dehydrating agents are, for example, dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide, or 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide; suitable catalysts are, for example, 4-dimethylaminopyridine (DMAP), piperidine, 3-methylpiperidine, or triethylamine.

[0150] In step (b) of the method of the present invention, the molar amount of catalyst may be intermediate product (A). The molar amount of the dehydrating agent is 1-10%, preferably 5-10%. The molar amount of the dehydrating agent is 100-150% of M-SH, preferably 120-140%. The molar ratio of intermediate product (A) to raw material (C) is 1:1.1-1:3, preferably 1:1.1-1:2, more preferably 1:1.2-1:2.

[0151] Step (b) of the method of the present invention is generally carried out in a solvent, preferably an organic solvent. There are no particular restrictions on the type of solvent, as long as it can dissolve the reactants, dehydrating agent, and catalyst and is chemically inert to the reaction, i.e., does not participate in the reaction. Examples of solvents commonly used are dimethyl sulfoxide, dichloromethane, ethyl acetate, tetrahydrofuran, and N,N-dimethylformamide. Preferably, the reaction is carried out in dichloromethane.

[0152] More specifically, in step (b) of the method of the present invention, intermediate product (A) is... Raw material (C) The catalyst, dissolved in a suitable amount of solvent, is added to the reaction vessel. Then, the dehydrating agent, dissolved in the same solvent, is transferred to a dropping funnel and subsequently added dropwise to the reaction vessel. The reaction is continued with stirring at -20°C to 40°C, preferably -10°C to 30°C, for 0.5-10 hours, preferably 1-8 hours. The solvent is removed by vacuum distillation to obtain the crude product, which is then separated by silica gel column chromatography to obtain product (B).

[0153] The amphiphilic polyetherified α-keto(hetero)aryl thioester compounds of general formula (I) of this invention, when used as initiators for LED photopolymerization, exhibit good absorption performance in the visible light region above 400 nm, which can be well matched with the wavelength of LED light sources. In particular, the photoinitiator of this invention shows good initiation performance under an LED light source at 405 nm, and can effectively initiate the photopolymerization reaction of aqueous or oil-based photopolymerizable monomers, especially aqueous or oil-based (meth)acrylate monomers. This avoids the use of expensive metal catalysts and features a simple synthesis route and low synthesis cost, thus possessing extremely high practical value.

[0154] Therefore, according to a third aspect of the present invention, a photopolymerizable composition is provided, comprising:

[0155] (A) At least one monomer or oligoolefin is an unsaturated photopolymerizable compound, and

[0156] (B) At least one amphiphilic polyetherified α-ketone(hetero)aryl thioester of general formula (I) as defined above

[0157] Compounds.

[0158] The amount of the amphiphilic polyetherified α-keto(hetero)aryl thioester compound of general formula (I) of the present invention is generally 0.01-10% by weight, preferably 0.05-6% by weight, such as 0.1-5% by weight, based on the total weight of the photopolymerizable composition.

[0159] The unsaturated compound (A) may contain, for example, one or more olefinic unsaturated double bonds, having a low molecular weight (monomer) or a relatively high molecular weight (oligomer).

[0160] Suitable oligomers may be epoxy (meth)acrylic resins, polyurethane (meth)acrylic resins, polyester (meth)acrylic resins, polyether (meth)acrylic resins, or acrylated poly (meth)acrylic resins.

[0161] Suitable monomers may be the following monofunctional compounds: (meth)acrylic acid and its salts; (meth)acrylates, such as alkyl esters like methyl, ethyl, 2-chloroethyl, N,N-dimethylaminoethyl, n-butyl, isobutyl, pentyl, hexyl esters, hydroxyalkyl esters like 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl esters, epoxyalkyl esters like glycidyl, 2,3-epoxybutyl, 3,4-epoxybutyl, 2,3-epoxycyclohexyl, 10,11-epoxyundecyl esters; (meth)acrylamides, N-substituted (meth)acrylamides, such as N- Hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-hexylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-cyclohexylmethacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-phenylmethylacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenylmethacrylamide, N-ethyl-N-phenylacrylamide, N-ethyl-N-phenylmethylacrylamide, N-(4-hydroxyphenyl) (Methyl)acrylamide and N-(4-hydroxyphenyl)methacrylamide; (meth)acrylonitrile; unsaturated acid anhydrides, such as itaconic anhydride, maleic anhydride, 2,3-dimethylmaleic anhydride, 2-chloromaleic anhydride; unsaturated esters, such as maleic acid esters; styrene, such as methylstyrene, chloromethylstyrene and o-, m- and p-hydroxystyrene, divinylbenzene; vinyl ethers, such as isobutyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, octyl vinyl ether and phenyl vinyl ether. Elemental ethers; vinyl and allyl esters, such as vinyl acetate, vinyl acrylate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate, divinyl succinate, diallyl phthalate, triallyl phosphate, vinyl chloride and vinylidene chloride; isocyanurates, such as triallyl isocyanurate and tris(2-acryloylethyl) isocyanurate; N-vinyl heterocyclic compounds, such as N-vinylpyrrolidone or substituted N-vinylpyrrolidone, N-vinylcaprolactam or substituted N-vinylcaprolactam, N-vinylcarbazole or N-vinylpyridine.

[0162] Suitable monomers can also be bifunctional or higher-functionality compounds, such as diacrylates, including 1,6-hexanediol diacrylate (HDDA), ethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate (TPGDA), neopentyl glycol diacrylate, hexamethylene glycol diacrylate, and bisphenol A diacrylate; trimethylolpropane triacrylate (TMPTA), trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate; tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate. Esters, pentaerythritol octaacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate, pentaerythritol octamethacrylate, pentaerythritol di-itaconate, dipentaerythritol tri-itaconate, dipentaerythritol penta-itaconate, dipentaerythritol hexa-itaconate, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diitaconate, sorbitol triacrylate, sorbitol tetraacrylate, pentaerythritol modified triacrylate, sorbitol tetramethacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, low-polyester acrylates and methacrylates, glycerol di- and tri-acrylates, 1,4-cyclohexane diacrylate, polyethylene glycol diacrylates and dimethacrylates with a molecular weight of 200-1500; or mixtures thereof.

[0163] In particular, the amphiphilic polyetherified α-keto(hetero)aryl thioester compounds of general formula (I) of the present invention are suitable for photopolymerization of (meth)acrylic compounds, preferably epoxy (meth)acrylic resins, polyurethane (meth)acrylic resins, polyester (meth)acrylic resins, polyether (meth)acrylic resins, acrylated poly(meth)acrylic resins, or (meth)acrylic esters as defined above that are monofunctional, bifunctional, or have higher functionality.

[0164] In addition to photoinitiators, photopolymerizable compositions may contain a variety of additives. Examples include thermal inhibitors designed to prevent premature polymerization, such as 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxo radicals and their derivatives; antistatic agents; flow improvers and tackifiers; and photopolymerization accelerators, such as amines, especially tertiary amines, such as tributylamine, triethanolamine, ethyl p-dimethylaminobenzoate, michalcone, N-methyldiethanolamine, N,N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine, diazabicyclooctane (triethylenediamine), 18-diazabicyclo[5]. 4.0] Undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and their salts; chain transfer agents; photosensitizers for altering or broadening spectral sensitivity, such as aromatic carbonyl compounds, such as benzophenone derivatives, thioxanthone derivatives, especially including isopropylthioxanthone, anthraquinone derivatives and 3-acylcoumarin derivatives, terphenyl, styryl ketones and 3-(aromatic acyl methylene)thiazoline, camphorquinone and eosin, rhodamine and erythrosine dyes; fillers; or pigments.

[0165] The photopolymerizable compositions of the present invention can be used for various purposes, such as as printing inks (e.g., screen printing inks, offset or flexographic printing inks, inkjet inks, sheet-fed printing inks, electrophotographic inks, gravure inks), as transparent coatings, white coatings, or colored coatings, for photographic reproduction methods, for holographic recording materials, for image recording methods or for producing printing plates that can be developed using organic solvents or aqueous alkaline media, for producing screen printing masks, as dental filling compounds, as adhesives, as pressure-sensitive adhesives, as laminating resins, as etching resists or permanent resists, as photostructured dielectrics and as soldering masks for electronic circuits, as resists for producing color filters for any type of display screen or for generating structures during the manufacture of plasma displays and electroluminescent displays, for producing optical switches and gratings, for manufacturing three-dimensional articles by bulk polymerization or according to stereolithography, for manufacturing composite materials of gel coatings and thick-layer compositions, for coating or sealing electronic components, or as coatings for optical fibers. The composition is also suitable for producing optical lenses (e.g., contact lenses or Fresnel lenses) and for manufacturing medical devices, auxiliaries, or implants.

[0166] In another aspect of the invention, the use of the amphiphilic polyetherified α-keto(hetero)aryl thioester compounds of general formula (I) of the invention as photoinitiators in photopolymerization is provided.

[0167] The amphiphilic polyetherified α-keto(hetero)aryl thioester compounds of general formula (I) of this invention exhibit excellent biocompatibility and are therefore suitable for the preparation of biopolymer materials. Suitable biopolymer materials may be polymers obtained from the photopolymerizable compositions described above.

[0168] Therefore, in another aspect of the invention, the use of the amphiphilic polyetherified α-keto(hetero)aryl thioester compounds of general formula (I) of the invention in the preparation of biopolymer materials is provided.

[0169] The beneficial effects of this invention are as follows: Compared with traditional photoinitiators, the amphiphilic polyetherified α-keto(hetero)aryl thioester compounds of general formula (I) of this invention can be better matched with the wavelength of LED light sources. In particular, the photoinitiator of this invention exhibits excellent initiation performance under a 405nm LED light source, and can effectively initiate the photopolymerization reaction of aqueous or oil-based photopolymerizable monomers, especially aqueous or oil-based (meth)acrylate monomers. It also avoids the use of expensive metal catalysts and has a simple synthesis route and low synthesis cost, thus possessing extremely high practical value.

[0170] Example

[0171] The present invention will be further described below with reference to specific embodiments, but should not be construed as limiting the scope of protection of the present invention.

[0172] Example 1: Synthesis of intermediate MO-TEA

[0173] The synthetic route for MO-TEA is as follows:

[0174]

[0175] 4-Methoxythiophenol (1.40 g, 10 mmol) was added to a 100 mL single-necked flask, followed by 20 mL of tetrahydrofuran, until completely dissolved. The flask was then placed in an ice-water bath at 0 °C. Oxaloyl chloride (1.51 g, 12 mmol) was dissolved in 30 mL of tetrahydrofuran and added to a dropping funnel at atmospheric pressure. Oxaloyl chloride was then added dropwise to the flask at a rate of 1-2 drops per second, maintaining the reaction temperature at 0 °C throughout. After the addition was complete, the reaction system was stirred for 10 h in an ice-water bath to terminate the reaction. Tetrahydrofuran was then removed by vacuum distillation. 30 mL of dichloromethane was added to the flask, followed by 10 mL of deionized water added dropwise while stirring at 25 °C. The mixture was then stirred vigorously for 1 h to terminate the reaction. The solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain the intermediate product MO-TEA.

[0176] 1 ¹H NMR (400 MHz, chloroform-d) δ 8.16 (s, 1H), 7.44–7.34 (m, 2H), 7.06–7.00 (m, 2H), 3.88 (s, 3H).

[0177] 13C NMR (100MHz, chloroform-d) δ 187.15, 161.46, 158.66, 135.65, 115.46, 115.29, 55.47.

[0178] Example 2: Synthesis of photoinitiator MO-TGTE

[0179] The synthetic route for MO-TGTE is as follows:

[0180]

[0181] MO-TEA (2.12 g, 10 mmol), triethylene glycol monomethyl ether (1.96 g, 12 mmol), and 4-dimethylaminopyridine (DMAP) (0.12 g, 1 mmol) were added to a 100 mL single-necked flask, followed by the addition of 30 mL of anhydrous dichloromethane to dissolve them. Dicyclohexylcarbodiimide (DCC) (2.47 g, 12 mmol) was dissolved in 20 mL of anhydrous dichloromethane and added to a dropping funnel at atmospheric pressure. The DCC dichloromethane solution was then added dropwise to the single-necked flask at a rate of 1-2 drops per second. After the addition was complete, the reaction system was stirred at 25 °C for 1 h. After the reaction was complete, the white solid impurities were removed by filtration, and the solution was retained. The reaction system was then purified by silica gel column chromatography to obtain the product, a yellow oily liquid product MO-TGTE.

[0182] 1 ¹H NMR (400MHz, chloroform-d) δ 7.36–7.32 (m, 2H), 6.99–6.95 (m, 2H), 4.50–4.46 (m, 2H), 3.83 (s, 3H), 3.73–3.61 (m, 8H), 3.57–3.52 (m, 2H), 3.37 (s, 3H).

[0183] 13 C NMR (100MHz, chloroform-d) δ 184.42, 161.18, 159.27, 135.85, 116.12, 115.22, 71.92, 70.77, 70.62, 70.58, 68.39, 66.39, 59.02, 55.39.

[0184] Example 3:

[0185] The purpose of Example 3 is to illustrate the light absorption performance of the photoinitiator MO-TGTE in Example 2.

[0186] The photoinitiator MO-TGTE from Example 2 was prepared to a concentration of 1×10⁻⁶. -4 mol L -1Anhydrous acetonitrile solution of this photoinitiator was used. The UV-Vis absorption curves of the anhydrous acetonitrile solution of this photoinitiator in the wavelength range of 200-500 nm were measured using a UV spectrophotometer.

[0187] The UV-Vis absorption spectrum of the photoinitiator MO-TGTE is as follows: Figure 2 As shown in the figure, this photoinitiator MO-TGTE has a certain absorption capacity in the visible light region above 400nm (see the values ​​shown in Table 1 below), and can be adapted to LED light sources.

[0188] Table 1

[0189]

[0190] Examples 4-6:

[0191] The purpose of Examples 4-6 is to demonstrate that the photoinitiator MO-TGTE of Example 2 can effectively initiate the photopolymerization reaction of (meth)acrylate monomers under irradiation with a 405nm LED light source.

[0192] 1. Preparation of photosensitive resin

[0193] Photosensitive solutions were prepared using three monomers: tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), and aqueous monomer polyethylene glycol (400) diacrylate (PEG(400)DA), along with the photoinitiator MO-TGTE from Example 2, in the following proportions:

[0194] Example 4:

[0195] Weigh appropriate amounts of the monomer tripropylene glycol diacrylate (TPGDA) and the photoinitiator MO-TGTE from Example 2 to prepare a photosensitive solution. The mass ratio of photoinitiator to monomer is photoinitiator:TPGDA = 1:100.

[0196] Example 5:

[0197] Weigh appropriate amounts of the monomer trimethylolpropane triacrylate (TMPTA) and the photoinitiator MO-TGTE from Example 2 to prepare a homogeneous photosensitive solution. The mass ratio of photoinitiator to monomer is photoinitiator:TMPTA = 1:100.

[0198] Example 6:

[0199] Weigh appropriate amounts of the aqueous monomer polyethylene glycol (400) diacrylate (PEG(400)DA) and the photoinitiator MO-TGTE from Example 2 to prepare a photosensitive solution. The mass ratio of photoinitiator to monomer is photoinitiator:PEG(400)DA = 1:100.

[0200] 2. Photopolymerization performance test

[0201] After applying appropriate amounts of the photosensitive solutions prepared in Examples 4-6 using capillaries, the solutions were evenly coated onto salt sheets made of KBr, with a thickness of approximately 30 μm. Another salt sheet was then placed on top of the first, and the two sheets were gently pressed together with tweezers to remove any air trapped between them, minimizing the influence of oxygen on the polymerization process. The photopolymerization kinetics were tested using a real-time infrared spectrometer (Thermo Fisher Scientific, Nicolet 5700), with an emission wavelength of 405 nm and a light intensity of 60 mW / cm². 2 .

[0202] Figure 3 The figures show the photopolymerization kinetics of three monomers initiated by the amphiphilic photoinitiator MO-TGTE, which contains an ether chain. This demonstrates that the amphiphilic polyetherified α-keto(hetero)aryl thioester initiator prepared in this invention can effectively initiate the photopolymerization of aqueous or oil-based photopolymerizable monomers, especially aqueous or oil-based (meth)acrylate monomers, under irradiation with a 405nm LED light source. This indicates that the photoinitiator of this invention has excellent initiation performance and applicability in LED photopolymerization systems.

Claims

1. An amphiphilic polyetherified α-keto(hetero)aryl thioester compound of general formula (I): (I) in: M represents or ; R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl group, -NO2, -CN, and C1-C, respectively. 20 Alkyl, C1-C 20 Alkyl, -CF3, -OCF3 or -OC6H5; L indicates ; Where R 15 It is H or C1-C4 alkyl; n is 0-10; m is 1-4.

2. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to claim 1, wherein: R 15 It is methyl; n is an integer between 0 and 4; m is an integer between 1 and 2.

3. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to claim 1, wherein R2, R3, R5, R6, R7, R8, and R9 are the same and are H; and R4 is methyl or methoxy.

4. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to any one of claims 1-3, wherein: R 15 It is methyl; n is 2; m is 1.

5. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to any one of claims 1-3, wherein the compound is: 。 6. A method for preparing amphiphilic polyetherified α-ketone(hetero)aryl thioester compounds according to any one of claims 1-5, comprising: (a) make and The reaction yields an intermediate product. ; as well as (b) make and The reaction, thereby obtaining , Where M, m, n and R 15 As defined in any one of claims 1-5.

7. The method according to claim 6, wherein the molar ratio of M-SH to oxaloyl chloride is 1:1.1-1:

2.

8. The method according to claim 7, wherein the molar ratio of M-SH to oxaloyl chloride is 1:1.2-1:

2.

9. The method according to claim 8, wherein the molar ratio of M-SH to oxaloyl chloride is 1:1.2-1:1.

8.

10. The method according to claim 6, wherein the molar ratio of intermediate product (A) to raw material (C) is 1:1.1-1:

3.

11. The method according to claim 7, wherein the molar ratio of intermediate product (A) to raw material (C) is 1:1.1-1:

2.

12. The method according to claim 9, wherein the molar ratio of intermediate product (A) to raw material (C) is 1:1.2-1:

2.

13. The method according to any one of claims 6-12, wherein the reaction in step (b) is carried out in the presence of one or more catalysts selected from the group consisting of 4-dimethylaminopyridine, piperidine, 3-methylpiperidine and triethylamine; and / or the molar amount of the catalyst is 1-10% of the intermediate product (A).

14. The method according to claim 13, wherein the catalyst in step (b) is 4-dimethylaminopyridine; and / or the molar amount of the catalyst is 5-10% of the intermediate product (A).

15. The method according to any one of claims 6-12, wherein the reaction in step (b) is carried out in the presence of one or more dehydrating agents selected from the group consisting of: dicyclohexylcarbodiimide, diisopropylcarbodiimide and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide; and / or the molar amount of the dehydrating agent is 100-150% of the intermediate product (A).

16. The method of claim 15, wherein the dehydrating agent in step (b) is dicyclohexylcarbodiimide; and / or the molar amount of the dehydrating agent is 120-140% of the intermediate product (A).

17. A photopolymerizable composition comprising: (A) At least one monomer or oligoolefin is an unsaturated photopolymerizable compound, and (B) At least one amphiphilic polyetherified α-ketone(hetero)aryl thioester compound obtained by the method of any one of claims 1-5 or any one of claims 6-16.

18. Use of amphiphilic polyetherified α-keto(hetero)aryl thioester compounds obtained by any one of claims 1-5 or any one of claims 6-16 as photoinitiators in photopolymerization.

19. Use of the amphiphilic polyetherified α-keto(hetero)aryl thioester compounds obtained by any one of claims 1-5 or any one of claims 6-16 in the preparation of biopolymer materials.

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