Amphiphilic polyetherified α-keto(hetero)aryl thioester compound for LED photopolymerization, preparation therefor and use thereof

Abstract

Disclosed in the present invention are an amphiphilic polyetherified α-keto(hetero)aryl thioester compound for LED photopolymerization, a preparation method therefor and a use thereof. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound of the present invention can be used as an initiator for LED photopolymerization, has good absorption performance in a visible light region of 400 nm or above, particularly shows good initiation performance under an LED light source of 405 nm, can effectively initiate photopolymerization of a water-based or oil-based photopolymerizable monomer, especially a water-based or oil-based (methyl)acrylate monomer, and can avoid the use of a precious metal catalyst, the synthesis route is simple, and the synthesis cost is low; thus, the present invention has extremely high practical value.

Description

Amphiphilic polyetherified α-ketone (hetero)aryl thioester compounds for LED photopolymerization and their preparation and application Technical Field

[0001] The present 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, particularly for LED photopolymerization. The present invention also relates to the preparation and application of amphiphilic polyetherified α-keto(hetero)aryl thioester compounds. Background Art

[0002] With the continuous development of LED photopolymerization technology, in order to meet the demand for its widespread application, it is necessary to develop photoinitiators suitable for LED light sources. Some such photoinitiators already exist in the prior art, such as CN104817653A, which discloses a coumarin aldoxime ester compound suitable for UV-LED light source curing, and CN102492059A, which discloses substituted diphenyl sulfide ketoxime ester photoinitiators. However, the LED photoinitiators reported so far often contain highly conjugated groups in their molecular structures. Therefore, the steps required to synthesize such photoinitiators are complex, which brings inconvenience to actual production applications.

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

[0004] In view of this, the research and development of new amphiphilic photoinitiators that can be used as LED light sources and have simple structures and synthetic routes remains one of the core tasks in this field. In addition, photopolymers, especially poly(meth)acrylates, are widely used in fields such as biomedical materials due to their excellent mechanical properties, good reprocessability and weather resistance. Therefore, the development of water-oil amphiphilic photoinitiators that can effectively polymerize water-based or oil-based photopolymerizable monomers, especially water-based or oil-based (meth)acrylate monomers, is also urgently needed in the field of photopolymerization.

[0005] Summary of the Invention

[0006] To promote the development of LED photopolymerization technology, the present inventors have been committed to promoting and applying LED photopolymerization technology, particularly researching and developing more photoinitiators suitable for LED photopolymerization. In light of the shortcomings of the existing technology, the present inventors have conducted extensive and in-depth research on photoinitiators suitable for LED photopolymerization, aiming to identify a novel, highly efficient, water- and oil-based amphiphilic photoinitiator that can effectively initiate the photopolymerization of aqueous or oil-based photopolymerizable monomers, particularly aqueous or oil-based (meth)acrylate monomers, while avoiding the use of precious metal catalysts and requiring a simple synthetic route.

[0007] The inventors surprisingly discovered that by simultaneously introducing an α-carbonyl ketone and an aryl or heteroaryl thioester group into a single molecule and then performing polyetherification, they have synthesized a novel class of highly efficient polyetherified α-keto(hetero)aryl thioester LED photoinitiators. The prepared initiator exhibits excellent absorption properties in the visible light region above 400 nm, effectively matching the wavelength of LED light sources. In particular, the photoinitiator of the present invention exhibits excellent initiation performance under a 405 nm LED light source, effectively initiating photopolymerization reactions of aqueous or oily photopolymerizable monomers, particularly aqueous or oily (meth)acrylate monomers. This method avoids the use of precious metal catalysts, has a simple synthesis route, and is low in cost, thus possessing extremely high practical value.

[0008] The purpose of the present invention is achieved based on the above findings.

[0009] Therefore, an object of the present invention is to provide an amphiphilic polyetherified α-keto(hetero)aryl thioester compound, the absorption wavelength of which is not only suitable for LED light source polymerization, but also can effectively initiate the photopolymerization reaction of water-based or oily (meth)acrylate monomers, and the synthesis route is simple while avoiding the use of precious metal catalysts.

[0010] Another object of the present invention is to provide a method for preparing the amphiphilic polyetherified α-keto(hetero)aryl thioester compounds of the present invention.

[0011] Another object of the present invention is to provide the use of the amphiphilic polyetherified α-keto(hetero)aryl thioester compound of the present invention as a photoinitiator in LED photopolymerization.

[0012] The technical solutions for achieving the above-mentioned purpose of the present invention can be summarized as follows:

[0013] 1. An amphiphilic polyetherified α-keto(hetero)aryl thioester compound of general formula (I):

[0014] in:

[0015] M stands for C6-C18 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 the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally 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 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkaryl, C7-C 20 Alkaryloxy, C7-C 20 Alkarylthio or 5-18 membered heteroaryl 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 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkaryl, C7-C 20 Alkaryloxy, C7-C 20Alkarylthio or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0016] L means

[0017] where R 15 is H or C1-C4 alkyl, preferably methyl;

[0018] n is an integer of 0-10, preferably 0-4,

[0019] m is an integer of 1-4, preferably 1-2.

[0020] 2. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to item 1, wherein:

[0021] M stands for C6-C 18 aryl or a 5- to 18-membered heteroaryl group containing one or more heteroatoms selected from N, S and O,

[0022] Among them, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally 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 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio or C7-C 20 Alkaryl; 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 20Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio or C7-C 20 The alkaryl group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate, or amino;

[0023] More preferably, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally 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 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; 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 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 The arylthio group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0024] More preferably, C6-C 18The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally 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 Halogenated alkyl, C1-C 20 Alkoxy, C1-C 20 Halogenated alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkylthio, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; wherein mono (C1-C6 alkyl) amino, di (C1-C6 alkyl) amino, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy and C6-C 18 The arylthio group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0025] More preferably, C6-C 18 Aryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted by one or more groups independently selected from the group consisting of halogen, hydroxy, -NO2, -CN, -COOH, -CHO, amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, -CF3, -OCF3 or -OC6H5.

[0026] 3. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to item 1 or 2, wherein:

[0027] M stands for C6-C 18 aryl or a 5- to 18-membered heteroaryl group containing one or more heteroatoms selected from N, S and O,

[0028] Among them, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with methyl or methoxy.

[0029] 4. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to any one of items 1 to 3, wherein:

[0030] M stands for

[0031] wherein R1 is selected from O, S or -NR 10 -;

[0032] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl, -NO2,

[0033] -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 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkaryl, C7-C 20 Alkaryloxy, C7-C 20 Alkarylthio or 5-18 membered heteroaryl 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 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkaryl, C7-C 20 Alkaryloxy, C7-C 20Alkarylthio or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0034] R 10 represents hydrogen, C1-C 20 Alkyl, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 Alkaryl or 5-18 membered heteroaryl 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 Alkylcycloalkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 The alkaryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino.

[0035] 5. The amphiphilic polyetherified α-ketone (hetero)aryl thioester compound according to item 4, wherein M represents wherein R2, R3, R4, R5, R6, R7, R8, and R9 are as defined in item 4.

[0036] 6. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to item 4 or 5, wherein:

[0037] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, 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 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C18 Aryloxy or C6-C 18 Arylthio; 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 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 The arylthio group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0038] More preferably,

[0039] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Halogenated alkyl, C1-C 20 Alkoxy, C1-C 20 Halogenated alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkylthio, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; wherein mono (C1-C6 alkyl) amino, di (C1-C6 alkyl) amino, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy and C6-C 18 The arylthio group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0040] More preferably,

[0041] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, C1-C 20 Alkyl, C1-C20 Alkoxy, -CF3, -OCF3 or -OC6H5;

[0042] Most preferably,

[0043] R2, R3, R5, R6, R7, R8, and R9 are the same and are H; R4 is methyl or methoxy.

[0044] 7. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to any one of items 1 to 6, wherein:

[0045] R 10 represents hydrogen, C1-C 20 Alkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 Alkaryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O; wherein C1-C 20 Alkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 The alkaryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino.

[0046] 8. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to any one of items 1 to 7, wherein:

[0047] R 15 is methyl;

[0048] n is 2;

[0049] m is 1.

[0050] 9. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to any one of items 1 to 8, which is:

[0051] 10. A method for preparing the amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to any one of items 1 to 9, comprising:

[0052] (a) Make and reaction to obtain an intermediate product as well as

[0053] (b) make and reaction, thereby obtaining

[0054] Where M, m, n and R 15 As defined in any one of items 1-9.

[0055] 11. The process 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.

[0056] 12. The process according to item 10 or 11, wherein the molar ratio of the intermediate product (A) to the raw material (C) is 1:1.1-1:3, preferably 1:1.1-1:2, more preferably 1:1.2-1:2.

[0057] 13. A process according to any one of items 10 to 12, wherein the reaction of 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%, preferably 5-10%, based on the intermediate product (A).

[0058] 14. The process according to any one of items 10 to 13, wherein the reaction of 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%, preferably 120-140%, based on the intermediate product (A).

[0059] 15. A photopolymerizable composition comprising:

[0060] (A) at least one monomeric or oligomeric ethylenically unsaturated photopolymerizable compound, and

[0061] (B) at least one amphiphilic polyetherified α-keto(hetero)aryl thioester compound obtained according to any one of items 1 to 9 or any one of items 10 to 14.

[0062] 16. Use of the amphiphilic polyetherified α-keto(hetero)aryl thioester compound obtained according to any one of items 1 to 9 or the method of any one of items 10 to 14 as a photoinitiator in photopolymerization.

[0063] 17. Use of the amphiphilic polyetherified α-keto(hetero)aryl thioester compound obtained according to any one of items 1 to 9 or the method of any one of items 10 to 14 in the preparation of biopolymer materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0064] FIG1 is a diagram of the initiation mechanism of the photoinitiator provided by the present invention;

[0065] FIG2 is a UV-visible absorption spectrum of the photoinitiator MO-TGTE of Example 2;

[0066] Figure 3 is a photopolymerization kinetic diagram of the polymerization of oily monomers tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA) and water-based monomer polyethylene glycol (400) diacrylate (PEG (400) DA) initiated by the photoinitiator MO-TGTE in Example 2 under a 405 nm LED light source. DETAILED DESCRIPTION

[0067] The first aspect of the present invention provides an amphiphilic polyetherified α-keto(hetero)aryl thioester compound of general formula (I):

[0068] in:

[0069] M stands for 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 the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally 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 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkaryl, C7-C 20 Alkaryloxy, C7-C 20 Alkarylthio or 5-18 membered heteroaryl 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 20Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkaryl, C7-C 20 Alkaryloxy, C7-C 20 Alkarylthio or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0070] L means

[0071] where R 15 is H or C1-C4 alkyl, preferably methyl;

[0072] n is an integer of 0-10, preferably 0-4,

[0073] m is an integer of 1-4, preferably 1-2.

[0074] In the present invention, the prefix "C n -C m " in each case means that the number of carbon atoms contained in the group is n to m.

[0075] "Halogen" refers to fluorine, chlorine, bromine and iodine and combinations thereof. In the present invention, preferably halogen includes F, Cl or a combination thereof.

[0076] The term "C n -C m"Alkyl" is a saturated hydrocarbon radical having n to m, for example 1 to 20, preferably 1 to 12, more preferably 1 to 8, particularly preferably 1 to 6 and especially preferably 1 to 4, carbon atoms, which may be branched or unbranched. Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof, in particular 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 isomers thereof. C1- The C6 alkyl group may be methyl, ethyl, propyl, butyl, pentyl, hexyl and isomers thereof, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, etc. The C1-C4 alkyl group may be methyl, ethyl, propyl, butyl and isomers thereof, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc.

[0077] The term "C3-C m "Cycloalkyl" refers to a saturated alicyclic monocyclic group having 3 to m, for example 3-10, preferably 3-8, more preferably 5-6, ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.

[0078] The term "C4-C m "Cycloalkylalkyl" means an alkyl group substituted by 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. The definitions of alkyl and cycloalkyl apply as described herein, and examples include cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclobutylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl, and the like.

[0079] The term "C4-C m"Alkylcycloalkyl" means a cycloalkyl group substituted by 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. The definitions of alkyl and cycloalkyl apply as described herein, and examples include methylcyclopropyl, ethylcyclopropyl, propylcyclopropyl, butylcyclopropyl, methylcyclobutyl, ethylcyclobutyl, propylcyclobutyl, butylcyclobutyl, methylcyclopentyl, ethylcyclopentyl, propylcyclopentyl, butylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexyl, and the like.

[0080] The term "C6-C 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. m As examples of the aryl group, there can be mentioned phenyl, azulenyl, cycloheptatrienyl, biphenyl, dicyclopentaphenyl, fluorenyl, phenanthrenyl, terphenyl, pyrenyl, naphthacene, yl, anthracenyl, indenyl, pentalenyl and naphthyl.

[0081] "5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O" is understood to mean 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 to 3, for example 1 or 2 heteroatoms. More preferably, the heteroaryl group is a ring system having two or three fused rings, which has 8-14, 9-14 or 9-13 ring members. Examples of heteroaryl groups include thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, furanyl, dibenzofuranyl, benzofuranyl, chromenyl, xanthenyl, thioxanthenyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolinyl, quinolinyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, phenanthridinyl, acridinyl, perylene, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isothiazolyl, isothiazin ... Azolyl, furazanyl, phenanthracene oxazinyl, 7-phenanthrenyl, anthraquinone-2-yl (= 9,10-dioxo-9,10-dihydroanthracen-2-yl), 3-benzo[b]thienyl, 5-benzo[b]thienyl, 2-benzo[b]thienyl, 4-dibenzofuranyl, 4-7-dibenzofuranyl, 4-methyl-7-dibenzofuranyl, 2-xanthenyl, 8-methyl-2-xanthenyl, 3-xanthenyl, phenanthrenyl, Thiol, 2,7-phen Thiyl, 2-pyrrolyl, 3-pyrrolyl, 5-methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl, 2-ethyl-4-imidazolyl, 2-ethyl-5-imidazolyl, 1H-tetrazol-5-yl, 3-pyrazolyl, 1-methyl-3-pyrazolyl, 1-propyl-4-pyrazolyl, 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl, 2-indolizinyl, 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-quinolizinyl, 3-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 3-methoxy-6-isoquinolyl, 2-quinolyl, 6-quinolyl, 7-quinolyl, 2-methoxy-3-quinolyl, 2-methoxy-6-quinolyl, 6-phthalazinyl, 7-phthalazinyl, 1-methoxy-6-phthalazinyl, 1, 4-dimethoxy-6-phthalazinyl, 1,8-naphthyridin-2-yl, 2-quinoxalinyl, 6-quinoxalinyl, 2,3-dimethyl-6-quinoxalinyl, 2,3-dimethoxy-6-quinoxalinyl, 2-quinazolinyl, 7-quinazolinyl, 2-dimethylamino-6-quinazolinyl, 3-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 3-methoxy-7-cinnolinyl, 2-pteridinyl, 6-pteridinyl, 7-pteridinyl, 6,7-dimethoxy-2-pteridinyl, 2-carbazolyl, 3-carbazolyl, 9-methyl 1-Methyl-2-carbazolyl, 9-methyl-3-carbazolyl, β-carbolin-3-yl, 1-methyl-β-carbolin-3-yl, 1-methyl-β-carbolin-6-yl, 3-phenanthridinyl, 2-acridinyl, 3-acridinyl, 2-perylene-1, 1-methyl-5-perylene-1, 5-phenanthrolinyl, 6-phenanthrolinyl, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenothiazinyl, 3-phenothiazinyl, 10-methyl-3-phenothiazinyl, 3-isothiazolyl, Azolyl, 4-iso Azolyl, 5-iso Azolyl, 4-methyl-3-furazanyl, 2-phenanthracene Oxazine, 10-methyl-2-phenanthracene Azinyl, etc.

[0082] The term "C7-C m "Aralkyl" means an alkyl group substituted by an aryl group and containing 7 to m, for example 7-20, preferably 7-12 carbon atoms in total. Alkyl and aryl are as defined herein, examples include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and the like.

[0083] The term "C7-C m"Alkaryl" means an aryl group substituted by an alkyl group and containing 7 to m, such as 7-20, preferably 7-12 carbon atoms in total. The definitions of alkyl and aryl apply as herein, and examples include methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, methylnaphthyl, ethylnaphthyl, and the like.

[0084] The term "C n -C m "Alkoxy" refers to n -C m Alkyl corresponding open chain C n -C m Any carbon atom of an alkane is bonded with an oxygen atom as a linker. n -C m Alkyl groups, such as C1-C 20 Alkoxy, preferably C1-C 12 Alkoxy, more preferably C1-C8 alkoxy, particularly preferably C1-C6 alkoxy. Examples include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy and isomers thereof, in particular methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy and isomers thereof. C1-C4 alkoxy may be methoxy, ethoxy, propoxy, butoxy and isomers thereof, in particular methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and the like.

[0085] The term "C4-C m "Cycloalkylalkoxy" refers to an alkoxy group substituted by a cycloalkyl group and containing a total of 4 to m carbon atoms, for example 4-20, preferably 4-12 carbon atoms, more preferably 4-10 carbon atoms. The definition of cycloalkyl applies herein. Examples include cyclopropylmethoxy, cyclopropylethoxy, cyclopropylpropoxy, cyclopropylbutoxy, cyclobutylmethoxy, cyclobutylethoxy, cyclobutylpropoxy, cyclobutylbutoxy, cyclopentylmethoxy, cyclopentylethoxy, cyclopentylpropoxy, cyclopentylbutoxy, cyclohexylmethoxy, cyclohexylethoxy, cyclohexylpropoxy, cyclohexylbutoxy and the like.

[0086] The term "C6-C m "Aryloxy" refers to a C6-C m The C6-C m Any aromatic carbon atom in an aromatic hydrocarbon is bonded to an oxygen atom as a linker. m Aryl groups, such as phenoxy, tolyloxy, naphthoxy and the like.

[0087] The term "C7-C m "Aralkyloxy" refers to a C7-Cm The alkyl carbon atom corresponding to the aralkyl group is bonded with an oxygen atom as a linking group. m Aralkyl groups include benzyloxy, phenethoxy, naphthylmethoxy, naphthylethoxy and the like.

[0088] The term "C7-C m "Alkaryloxy" refers to a C7-C m The aryl carbon atom corresponding to the alkaryl group is bonded with an oxygen atom as a linking group. m Alkaryl groups, examples include methylphenoxy, dimethylphenoxy, trimethylphenoxy, ethylphenoxy, diethylphenoxy, triethylphenoxy, methylnaphthyloxy, ethylnaphthyloxy and the like.

[0089] The term "C n -C m "Alkylthio" refers to a C n -C m Alkyl corresponding open chain C n -C m Any carbon atom of an alkane is bonded with a sulfur atom as a linker. n -C m Alkyl groups, such as C1-C 20 Alkylthio, preferably C1-C 12 Alkylthio, more preferably C1-C8 alkylthio, 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 isomers thereof. C1-C4 alkylthio may include methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio, tert-butylthio and the like.

[0090] The term "C4-C m The term "cycloalkylalkylthio" refers to an alkylthio group substituted by a cycloalkyl group and containing 4 to m carbon atoms, for example 4-20, preferably 4-12 carbon atoms, more preferably 4-10 carbon atoms in total. The definitions of cycloalkyl and alkylthio apply herein. Examples include cyclopropylmethylthio, cyclopropylethylthio, cyclopropylpropylthio, cyclopropylbutylthio, cyclobutylmethylthio, cyclobutylethylthio, cyclobutylpropylthio, cyclobutylbutylthio, cyclopentylmethylthio, cyclopentylethylthio, cyclopentylpropylthio, cyclopentylbutylthio, cyclohexylmethylthio, cyclohexylethylthio, cyclohexylpropylthio, cyclohexylbutylthio and the like.

[0091] The term "C6-C m "Arylthio" refers to a C6-C m The C6-C mA C6-C m Aryl groups, such as phenylthio, tolylthio, naphthylthio and the like.

[0092] The term "C7-C m "Aralkylthio" refers to a C7-C m The alkyl carbon atom corresponding to the aralkyl group is bonded with a sulfur atom as a linking group. m Aralkyl groups include benzylthio, phenethylthio, naphthylmethylthio, naphthylethylthio and the like.

[0093] The term "C7-C m "Alkarylthio" refers to a C7-C m The aryl carbon atom corresponding to the alkaryl group is bonded with a sulfur atom as a linking group. m Alkaryl groups, examples include methylphenylthio, dimethylphenylthio, trimethylphenylthio, ethylphenylthio, diethylphenylthio, triethylphenylthio, methylnaphthylthio, ethylnaphthylthio and the like.

[0094] “C1-C 20 "Haloalkyl" includes C1-C 12 Halogenated alkyl, C1-C8 haloalkyl, C1-C6 haloalkyl, C1-C4 haloalkyl. The halogen and alkyl in the haloalkyl are as defined herein.

[0095] “C1-C 20 "Haloalkoxy" includes C1-C 12 Halogenated alkoxy, C1-C8 haloalkoxy, C1-C6 haloalkoxy, C1-C4 haloalkoxy. The halogen and alkoxy in the haloalkoxy are as defined herein for halogen and alkoxy.

[0096] “C1-C 20 "Haloalkylthio" includes C1-C 12 Halogenated alkylthio, C1-C8 haloalkylthio, C1-C6 haloalkylthio, C1-C4 haloalkylthio. The halogen and alkylthio in the haloalkylthio are as defined herein for halogen and alkoxy.

[0097] In a preferred embodiment of the present invention,

[0098] M stands for C6-C 18 aryl or a 5- to 18-membered heteroaryl group containing one or more heteroatoms selected from N, S and O,

[0099] Among them, C6-C 18The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally 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 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio or C7-C 20 Alkaryl; 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 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio or C7-C 20 The alkaryl group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate, or amino;

[0100] More preferably, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally 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-C20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; 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 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 The arylthio group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0101] More preferably, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally 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-C6 alkyl, 20 Alkyl, C1-C 20 Halogenated alkyl, C1-C 20 Alkoxy, C1-C 20 Halogenated alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkylthio, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; wherein mono (C1-C6 alkyl) amino, di (C1-C6 alkyl) amino, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy and C6-C 18 The arylthio group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0102] More preferably, C6-C 18 Aryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted by one or more groups independently selected from the group consisting of halogen, hydroxy, -NO2, -CN, -COOH, -CHO, amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, -CF3, -OCF3 or -OC6H5;

[0103] Most preferably, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with methyl or methoxy.

[0104] In a preferred embodiment of the present invention,

[0105] M stands for

[0106] wherein R1 is selected from O, S or -NR 10 -;

[0107] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, 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 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkaryl, C7-C 20 Alkaryloxy, C7-C 20 Alkarylthio or 5-18 membered heteroaryl 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 20Alkoxy, C1-C 20 Alkylthio, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Cycloalkylalkoxy, C4-C 20 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkaryl, C7-C 20 Alkaryloxy, C7-C 20 Alkarylthio or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0108] R 10 represents hydrogen, C1-C 20 Alkyl, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 Alkaryl or 5-18 membered heteroaryl 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 Alkylcycloalkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 The alkaryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino.

[0109] In a preferred embodiment of the present invention,

[0110] M stands for in:

[0111] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, 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 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkaryl, C7-C 20 Alkaryloxy, C7-C 20 Alkarylthio or 5-18 membered heteroaryl 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 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkaryl, C7-C 20 Alkaryloxy, C7-C 20 The alkarylthio group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, mercapto, carboxyl, sulfonic acid, carboxylate or amino.

[0112] In a more preferred embodiment of the present invention,

[0113] M stands for in:

[0114] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, 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 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; 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 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 The arylthio group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0115] More preferably,

[0116] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Halogenated alkyl, C1-C 20 Alkoxy, C1-C 20 Halogenated alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkylthio, C3-C 10 Cycloalkyl, C6-C 18Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; wherein mono (C1-C6 alkyl) amino, di (C1-C6 alkyl) amino, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy and C6-C 18 The arylthio group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino;

[0117] More preferably,

[0118] R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, -CF3, -OCF3 or -OC6H5;

[0119] Most preferably,

[0120] R2, R3, R5, R6, R7, R8, and R9 are the same and are H; R4 is methyl or methoxy.

[0121] In a preferred embodiment of the present invention,

[0122] R 10 represents hydrogen, C1-C 20 Alkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 Alkaryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O; wherein C1-C 20 Alkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 The alkaryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino.

[0123] In a preferred embodiment of the present invention, M is wherein R2, R3, R5 and R6 are the same and are H; and R4 is methyl or methoxy.

[0124] In another preferred embodiment of the present invention, M is wherein R2, R3, R5, R6, R7, R8, and R9 are the same and are H.

[0125] In a particularly preferred embodiment of the present invention, R 15 is methyl; n is 2; m is 1.

[0126] As specific examples of the amphiphilic polyetherified α-keto(hetero)aryl thioester compounds of the general formula (I), there can be mentioned

[0127] The second aspect of the present invention relates to a method for preparing an amphiphilic polyetherified α-keto(hetero)aryl thioester compound of the general formula (I) of the present invention, comprising:

[0128] (a) Make and reaction to obtain an intermediate product as well as

[0129] (b) make and reaction, thereby obtaining

[0130] Where M, m, n and R 15 As defined above.

[0131] In step (a) of the method of the present invention, 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.

[0132] Step (a) of the method of the present invention is typically carried out in a solvent, preferably an organic solvent. There are no particular restrictions on the type of solvent, as long as it dissolves the reactants and is chemically inert to the reaction, i.e., does not participate in the reaction. Examples of solvents commonly used include dichloromethane, ethyl acetate, tetrahydrofuran, and N,N-dimethylformamide. Preferably, the reaction in step (a) is carried out in tetrahydrofuran.

[0133] 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, and then dropped into the above reaction vessel, and the reaction is stirred at -10 to 20° C., preferably in an ice-water bath, for 2-12 hours, preferably 4-10 hours; then an appropriate amount of deionized water is added to the reaction system, and vigorous stirring is continued for 0.5-4 hours, preferably 1-3 hours. After the reaction is completed, the aqueous phase is separated, and the solvent is removed by distillation under reduced pressure to obtain a crude product, which is separated by silica gel column chromatography to obtain the intermediate product (A).

[0134] 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 include, for example, dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide, or 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide; suitable catalysts include, for example, 4-dimethylaminopyridine (DMAP), piperidine, 3-methylpiperidine, or triethylamine.

[0135] In step (b) of the process of the present invention, the molar amount of the catalyst may be The molar amount of the dehydrating agent is 100-150% of M-SH, preferably 120-140%. The molar ratio of the intermediate product (A) to the raw material (C) is 1:1.1-1:3, preferably 1:1.1-1:2, and more preferably 1:1.2-1:2.

[0136] Step (b) of the method of the present invention is typically carried out in a solvent, preferably an organic solvent. There are no particular restrictions on the choice of solvent type, 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 include dimethyl sulfoxide, dichloromethane, ethyl acetate, tetrahydrofuran, and N,N-dimethylformamide. Preferably, the reaction is carried out in dichloromethane.

[0137] More specifically, in step (b) of the process of the present invention, the intermediate product (A) Raw materials (C) The catalyst is dissolved in an appropriate amount of solvent and added to a reaction vessel. The dehydrating agent is then dissolved in the same solvent and transferred to a dropping funnel. The mixture is then added dropwise to the reaction vessel. The reaction is continued by stirring at -20°C to 40°C, preferably -10°C to 30°C. The reaction time can be 0.5-10 hours, preferably 1-8 hours. The solvent is removed by distillation under reduced pressure to obtain a crude product, which is then separated by silica gel column chromatography to obtain product (B).

[0138] The amphiphilic polyetherified α-keto(hetero)aryl thioester compounds of the general formula (I) of the present invention are used as initiators for LED photopolymerization. They exhibit excellent absorption properties in the visible light region above 400 nm, effectively matching the wavelength of LED light sources. In particular, the photoinitiators of the present invention exhibit excellent initiation performance under a 405 nm LED light source, effectively initiating photopolymerization reactions of aqueous or oily photopolymerizable monomers, particularly aqueous or oily (meth)acrylate monomers. Furthermore, the compounds avoid the use of precious metal catalysts, have a simple synthesis route, and are low in cost, thus possessing extremely high practical value.

[0139] Therefore, according to a third aspect of the present invention, there is provided a photopolymerizable composition comprising:

[0140] (A) at least one monomeric or oligomeric ethylenically unsaturated photopolymerizable compound, and

[0141] (B) at least one amphiphilic polyetherified α-keto(hetero)aryl thioester compound of the general formula (I) as defined above.

[0142] The amount of the amphiphilic polyetherified α-keto(hetero)aryl thioester compound of formula (I) of the present invention is usually 0.01-10 wt %, preferably 0.05-6 wt %, such as 0.1-5 wt %, based on the total weight of the photopolymerizable composition.

[0143] The unsaturated compounds (A) may contain, for example, one or more ethylenically unsaturated double bonds and have a low molecular weight (monomers) or a relatively high molecular weight (oligomers).

[0144] Suitable oligomers may be epoxy (meth)acrylate resins, polyurethane (meth)acrylate resins, polyester (meth)acrylate resins, polyether (meth)acrylate resins or acrylated poly (meth)acrylate resins.

[0145] Suitable monomers may be the following monofunctional compounds: (meth)acrylic acid and its salts; (meth)acrylic acid esters, for example alkyl esters such as methyl, ethyl, 2-chloroethyl, N,N-dimethylaminoethyl, n-butyl, isobutyl, pentyl, hexyl esters, hydroxyalkyl esters such as 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl esters, epoxyalkyl esters such as glycidyl, 2,3-epoxybutyl, 3,4-epoxybutyl, 2,3-epoxycyclohexyl, 10,11-epoxyundecyl esters; (meth)acrylamide, N-substituted (meth)acrylamide, for example N- Methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-hexylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-cyclohexylmethacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenylmethacrylamide, N-ethyl-N-phenylacrylamide, N-ethyl-N-phenylmethacrylamide, N-(4-hydroxyphenyl)acrylamide unsaturated acid anhydrides such as itaconic anhydride, maleic anhydride, 2,3-dimethylmaleic anhydride, 2-chloromaleic anhydride; unsaturated esters such as maleic esters; styrenes 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 phenylvinyl ether vinyl ethers, 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.

[0146] Suitable monomers may also be difunctional or higher-functional compounds, for example diacrylates, such as 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, dipentaerythritol hexaacrylate. esters, tripentaerythritol octaacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritol diitaconate, dipentaerythritol triitaconate, dipentaerythritol pentaitaconate, dipentaerythritol hexaitaconate, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diitaconate, sorbitol triacrylate, sorbitol tetraacrylate, pentaerythritol-modified triacrylates, sorbitol tetramethacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, oligoester acrylates and methacrylates, glycerol di- and triacrylates, 1,4-cyclohexane diacrylate, diacrylates and dimethacrylates of polyethylene glycol having a molecular weight of 200-1500; or mixtures thereof.

[0147] In particular, the amphiphilic polyetherified α-keto(hetero)aryl thioester compounds of the 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 monofunctional, difunctional or higher functionality (meth) acrylates as defined above.

[0148] In addition to the photoinitiator, the photopolymerizable composition may contain various additives. Examples are thermal inhibitors intended to prevent premature polymerization, such as 2,2,6,6-tetramethyl-4-hydroxypiperidin-1-oxyl and its derivatives; antistatic agents; flow improvers and adhesion promoters; photopolymerization accelerators, such as amines, especially tertiary amines, such as tributylamine, triethanolamine, ethyl p-dimethylaminobenzoate, Michler's ketone, 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 its salts; chain transfer agents; photosensitizers for changing or broadening the spectral sensitivity, such as aromatic carbonyl compounds, such as benzophenone derivatives, thioxanthone derivatives, These include, in particular, isopropylthioxanthone, anthraquinone derivatives and 3-acylcoumarin derivatives, terphenyls, styryl ketones and 3-(aroylmethylene)thiazolines, camphorquinone, and also eosin, rhodamine and erythrosine dyes; fillers; or pigments.

[0149] The photopolymerizable compositions according to the invention can be used for various purposes, for example as printing inks (e.g. screen printing inks, offset or flexographic printing inks, inkjet inks, sheet-fed printing inks, electrophotographic inks, gravure inks), as clear, white or pigmented coatings, in photocopying processes, in holographic recording materials, in image recording processes or for producing printing plates that can be developed with organic solvents or with aqueous alkaline media, for producing masks for screen printing, as dental filling compounds, as adhesives, as pressure-sensitive adhesives, as laminating resins, as etch resists or permanent resists, as photostructurable dielectrics and as solder masks for electronic circuits, as resists for producing color filters for display screens of any type or for generating structures during the production of plasma and electroluminescent displays, for producing optical switches, gratings, for producing three-dimensional articles by bulk polymerization or according to stereolithography, for producing composite materials of gel coatings and thick-layer compositions, for coating or sealing electronic components or as coatings for optical fibers. The compositions are also suitable for producing optical lenses, such as contact lenses or Fresnel lenses, and for the manufacture of medical devices, aids or implants.

[0150] In another aspect of the present invention, there is provided use of the amphiphilic polyetherified α-keto(hetero)aryl thioester compound of the general formula (I) of the present invention as a photoinitiator in photopolymerization.

[0151] The amphiphilic polyetherified α-keto(hetero)aryl thioester compounds of the general formula (I) of the present invention have excellent biocompatibility and are therefore suitable for the preparation of biopolymer materials. Suitable biopolymer materials can be polymer materials obtained from the photopolymerizable composition described above.

[0152] Therefore, in another aspect of the present invention, there is provided use of the amphiphilic polyetherified α-keto(hetero)aryl thioester compound of the general formula (I) of the present invention in the preparation of biopolymer materials.

[0153] The present invention has the beneficial effect of better matching the wavelength of LED light sources with the amphiphilic polyetherified α-keto(hetero)aryl thioester compounds of the general formula (I) compared to conventional photoinitiators. In particular, the photoinitiators of the present invention exhibit excellent initiation performance under a 405nm LED light source, effectively initiating photopolymerization reactions of aqueous or oily photopolymerizable monomers, particularly aqueous or oily (meth)acrylate monomers. Furthermore, the invention avoids the use of precious metal catalysts, has a simple synthesis route, and is low in cost, thus possessing extremely high practical value.

[0154] Example

[0155] The present invention will be further described below with reference to specific embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0156] Example 1: Synthesis of intermediate MO-TEA

[0157] The synthetic route of MO-TEA is as follows:

[0158] 4-Methoxythiophenol (1.40 g, 10 mmol) was added to a 100 mL single-necked flask, along with 20 mL of tetrahydrofuran to dissolve it completely. The flask was then placed in an ice-water bath at 0°C. Oxalyl chloride (1.51 g, 12 mmol) was dissolved in 30 mL of tetrahydrofuran and added to a normal pressure dropping funnel. Oxalyl chloride was then added dropwise to the single-necked flask at a rate of 1-2 drops per second, maintaining the reaction temperature at 0°C. After the addition was complete, the reaction system was stirred for 10 hours in an ice-water bath to terminate the reaction. The tetrahydrofuran was then removed by vacuum distillation, and 30 mL of dichloromethane was added to the flask. 10 mL of deionized water was added dropwise to the reaction system at 25°C, followed by vigorous stirring for 1 hour 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.

[0159] 1 H 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).

[0160] 13C NMR (100 MHz, chloroform-d) δ 187.15, 161.46, 158.66, 135.65, 115.46, 115.29, 55.47.

[0161] Example 2: Synthesis of photoinitiator MO-TGTE

[0162] The synthetic route of MO-TGTE is as follows:

[0163] 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, and then 30 mL of anhydrous dichloromethane was added to the flask to dissolve it. Dicyclohexylcarbodiimide (DCC) (2.47 g, 12 mmol) was dissolved in 20 mL of anhydrous dichloromethane and added to a normal pressure dropping funnel. The dichloromethane solution of DCC 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 and reacted at 25 ° C for 1 hour. After the reaction was complete, the white solid impurities were filtered out and the solution was retained. The reaction system was then separated and purified using a silica gel column chromatography to obtain the product, obtaining MO-TGTE as a yellow oily liquid product.

[0164] 1 H NMR (400 MHz, 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).

[0165] 13 C NMR (100 MHz, 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.

[0166] Example 3:

[0167] The purpose of Example 3 is to illustrate the light absorption performance of the photoinitiator MO-TGTE in Example 2.

[0168] The photoinitiator MO-TGTE of Example 2 was prepared to a concentration of 1×10 -4 mol L -1The UV-visible absorption curve of the anhydrous acetonitrile solution of the photoinitiator in the wavelength range of 200-500 nm was tested using an ultraviolet spectrophotometer.

[0169] The UV-visible absorption spectrum of the photoinitiator MO-TGTE is shown in FIG2 ; it can be seen that the photoinitiator MO-TGTE has a certain absorption capacity in the visible light region above 400 nm (see the values ​​shown in Table 1 below), and is suitable for LED light sources.

[0170] Table 1

[0171] Example 4-6:

[0172] The purpose of Examples 4-6 is to illustrate that the photoinitiator MO-TGTE of Example 2 can effectively initiate the photopolymerization reaction of (meth)acrylate monomers under irradiation with a 405 nm LED light source.

[0173] 1. Prepare photosensitive resin

[0174] Three monomers, tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA) and water-based monomer polyethylene glycol (400) diacrylate (PEG (400) DA), and the photoinitiator MO-TGTE of Example 2 were selected and prepared according to the following proportions to prepare a photosensitive solution:

[0175] Example 4:

[0176] Appropriate amounts of monomer tripropylene glycol diacrylate (TPGDA) and the photoinitiator MO-TGTE of Example 2 were weighed separately to prepare a photosensitive solution, with the mass ratio of photoinitiator to monomer being photoinitiator:TPGDA=1:100.

[0177] Example 5:

[0178] Appropriate amounts of monomer trimethylolpropane triacrylate (TMPTA) and the photoinitiator MO-TGTE of Example 2 were weighed separately to prepare a uniform photosensitive solution, with the mass ratio of photoinitiator to monomer being photoinitiator:TMPTA=1:100.

[0179] Example 6:

[0180] Appropriate amounts of aqueous monomer polyethylene glycol (400) diacrylate (PEG (400) DA) and the photoinitiator MO-TGTE of Example 2 were weighed separately to prepare a photosensitive solution, and the mass ratio of photoinitiator to monomer was photoinitiator: PEG (400) DA = 1:100.

[0181] 2. Photopolymerization performance test

[0182] Using a capillary tube, appropriate amounts of the prepared photosensitive solutions in Examples 4-6 were uniformly applied to a KBr salt sheet to a thickness of approximately 30 μm. Another layer of salt was then placed on top of the salt sheet. Tweezers were used to gently press the two salt sheets together to expel the air between them and minimize the effects of oxygen on polymerization. Photopolymerization kinetics were measured using a real-time infrared spectrometer (Nicolet 5700, Thermo Fisher Scientific, USA). The light source used had an emission wavelength of 405 nm and a light intensity of 60 mW / cm 2 .

[0183] Figure 3 shows the photopolymerization kinetics of three monomers initiated by the ether-containing amphiphilic photoinitiator MO-TGTE. This demonstrates that the amphiphilic polyetherified α-keto(hetero)aryl thioester initiator prepared by the present invention can effectively initiate photopolymerization of aqueous or oil-based photopolymerizable monomers, particularly aqueous or oil-based (meth)acrylate monomers, under 405 nm LED light. This demonstrates that the photoinitiator of the present 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): in: M stands for C6-C 18 aryl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O, wherein C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally 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 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkyl, C7-C 20 Alkaryloxy, C7-C 20 alkylthio 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 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkyl, C7-C 20 Alkaryloxy, C7-C 20 The alkarylthio group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino; L stands for Where R 15 is H or C1-C4 alkyl, preferably methyl; n is an integer of 0-10, preferably 0-4, m is an integer of 1-4, preferably 1-2.

2. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to claim 1, wherein: M stands for C6-C 18 aryl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O, Among them, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally 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 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio or C7-C 20 Alkaryl; 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 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio or C7-C 20 The alkaryl group may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino; More preferably, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally 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 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; 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 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 The arylthio group may be optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino; More preferably, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally 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 Halogenated alkyl, C1-C 20 Alkoxy, C1-C 20 Halogenated alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkylthio, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy and C6-C 18 The arylthio group may be optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino; More preferably, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally 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 Alkoxy, -CF3, -OCF3 or -OC6H5.

3. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to claim 1 or 2, wherein: M stands for C6-C 18 aryl or a 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O, Among them, C6-C 18 The aryl group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with methyl or methoxy.

4. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to any one of claims 1 to 3, wherein: M stands for Wherein R1 is selected from O, S or -NR 10 -; R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, 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 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkyl, C7-C 20 Alkaryloxy, C7-C 20 alkylthio 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 Cycloalkylalkylthio, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy, C6-C 18 Arylthio, C7-C 20 Aralkyl, C7-C 20 Aralkyloxy, C7-C 20 Aralkylthio, C7-C 20 Alkyl, C7-C 20 Alkaryloxy, C7-C 20 The alkarylthio group or the 5-18 membered heteroaryl group containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino; R 10 Represents hydrogen, C1-C 20 Alkyl, C3-C 10 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Alkylcycloalkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 an alkylaryl group 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 Alkylcycloalkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 The alkaryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino.

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

6. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to claim 4 or 5, wherein: R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, 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 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; 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 Cycloalkylalkylthio, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 The arylthio group may be optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxyl, thiol, carboxyl, sulfonic acid, carboxylate or amino; further preferably, R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C1-C 20 Alkyl, C1-C 20 Halogenated alkyl, C1-C 20 Alkoxy, C1-C 20 Halogenated alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkylthio, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy or C6-C 18 Arylthio; wherein mono(C1-C6 alkyl)amino, di(C1-C6 alkyl)amino, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryloxy and C6-C 18 The arylthio group may be optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino; More preferably, R2, R3, R4, R5, R6, R7, R8, and R9 independently represent hydrogen, halogen, hydroxyl, -NO2, -CN, -COOH, -CHO, amino, C1-C 20 Alkyl, C1-C 20 Alkoxy, -CF3, -OCF3 or -OC6H5; Most preferably, R2, R3, R5, R6, R7, R8, and R9 are the same and are H; R4 is methyl or methoxy.

7. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to any one of claims 1 to 6, wherein: R 10 Represents hydrogen, C1-C 20 Alkyl, C6-C 18 Aryl, C7-C 20 Aralkyl, C7-C 20 an alkylaryl group 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 Aralkyl, C7-C 20 The alkaryl or 5-18 membered heteroaryl containing one or more heteroatoms selected from N, S and O may be optionally substituted with one or more groups independently selected from the group consisting of halogen, nitro, hydroxy, thiol, carboxyl, sulfonic acid, carboxylate or amino.

8. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to any one of claims 1 to 7, wherein: R 15 is methyl; n is 2; m is 1.

9. The amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to any one of claims 1 to 8, which is:

10. A method for preparing an amphiphilic polyetherified α-keto(hetero)aryl thioester compound according to any one of claims 1 to 9, comprising: (a) Make and Reaction to obtain the intermediate product as well as (b) Make and reaction, thereby obtaining Where M, m, n and R 15 As defined in any one of claims 1 to 9.

11. The method according to claim 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.

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

2.

13. The process according to any one of claims 10 to 12, wherein the reaction of 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%, preferably 5-10%, of the intermediate product (A).

14. The method according to any one of claims 10 to 13, wherein the reaction of 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%, preferably 120-140%, of the intermediate product (A).

15. A photopolymerizable composition comprising: (A) at least one monomeric or oligomeric ethylenically unsaturated photopolymerizable compound, and (B) at least one amphiphilic polyetherified α-keto(hetero)aryl thioester compound obtainable by the process according to any one of claims 1 to 9 or according to any one of claims 10 to 14.

16. Use of the amphiphilic polyetherified α-keto(hetero)aryl thioester compound obtained according to any one of claims 1 to 9 or according to any one of claims 10 to 14 as a photoinitiator in photopolymerization.

17. Use of the amphiphilic polyetherified α-keto(hetero)aryl thioester compound obtained according to the method of any one of claims 1 to 9 or any one of claims 10 to 14 in the preparation of biopolymer materials.

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