Carbazole photoinitiator, photopolymerizable composition and application

Abstract

The invention relates to a carbazole photoinitiator, a photopolymerizable composition and application. The carbazole photoinitiator is a compound with a structure as shown in a formula (1): # imgabs0 # R9 is a C3-C25 nitrogen-containing aromatic group containing a benzene ring structure doped with 1-3 N atoms. The nitrogen-containing heterocyclic ring is introduced to the carbazole ring, so that the solubility of the compound is improved, and the sensitivity of the photoinitiator to light is improved.

Description

Technical Field

[0001] The invention relates to the technical field of photoinitiators, and in particular to a carbazole photoinitiator, a photopolymerizable composition and applications. Background Art

[0002] Photocuring is a process in which a chemically active liquid material undergoes cross-linking polymerization under the action of light or electron beam to form a solid product. It is generally used in the film-forming process. After being irradiated by UV light or visible light, the photoinitiator in the photocurable material generates active initiating groups (free radicals or cations), which in turn cause the monomers or oligomers in the system to undergo polymerization and solidify into a dense cross-linked network. Compared with other curing technologies such as physical and chemical treatment, biological treatment and thermal treatment, photocuring has the advantages of fast curing speed, low energy consumption, less pollution, high economic benefits and wide adaptability.

[0003] Although the proportion of photoinitiators in the photocuring system is relatively low (usually 1%-5%), they are crucial for polymerization reactions under ultraviolet or visible light. Free radical photoinitiators can be further divided into two types: cleavage type (type I) and hydrogen abstraction type (type II). Oxime ester photoinitiators belong to the hydrogen abstraction type and are widely used because of their strong ultraviolet absorption, simple synthesis, low price and strong hydrogen abstraction ability. Its working mechanism is to extract a hydrogen from the hydrogen donor in the excited state to generate an inactive carbonyl radical and a highly active donor radical, which then initiates polymerization.

[0004] In photocuring technology, commonly used light sources include xenon lamps, mercury lamps, pulsed light sources and laser light sources. Traditional photocuring technology mostly uses medium-pressure or high-pressure mercury lamps, but mercury lamps have a short life (1500-2000 hours), high energy consumption, severe heat generation, and release of toxic mercury. In contrast, LED light sources, as new light sources, have the advantages of high energy conversion efficiency, long life, low environmental and health hazards, and can provide a narrow spectrum to meet specific application requirements. Therefore, it is particularly important to develop a photoinitiator with high initiation activity that is suitable for LED light sources and can be used as a single component. In view of this, the present invention provides a carbazole photoinitiator, a photopolymerizable composition and an application. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a carbazole photoinitiator, a photopolymerizable composition and application thereof, with the purpose of increasing the solubility and light sensitivity of the compound by introducing a nitrogen-containing heterocycle into the carbazole ring.

[0006] In a first aspect, a carbazole photoinitiator is a compound having a structure shown in formula (1):

[0007]

[0008] In formula (1), R 1 -R 8 are independently selected from hydrogen; or R 1 -R 8 Any two adjacent substituents in the 10 )=C(R 11 )-C(R 12 )=C(R 13 )-; or R 3 , R 6 Each independently selected from any one of the following structures: nitro, cyano, C 1 -C 15 Alkyl, C 1 -C 15 Alkoxy, C 1 -C 15 Alkylthio, C 1 -C 15 The alkyl ester group, C 3 -C 15 Cycloalkyl, C 3 -C 15 Heterocycloalkyl, C 6 -C 15 Aryl, C 4 -C 15 Heteroaryl, -MC(R 14 )=NOC(=O)-R 15 , -C(=O)-R 16 , halogen-substituted C 1 -C 15 Alkyl, C 1 -C 15 Alkoxy, C 1 -C 15 Alkylthio or C 1 -C 15 The alkyl ester group, substituted C 3 -C 15 Cycloalkyl, C 6 -C 15 The aromatic group, C 3 -C 15 Heterocycloalkyl or C 4 -C 15 The heteroaryl group, and R 3 , R 6 At least one of them is -MC(R 14 )=NOC(=O)-R 15 ;

[0009] R 9 A C containing a benzene ring structure doped with 1-3 N atoms 3 -C25 A nitrogen-containing aromatic group;

[0010] R 10 -R 13 Each independently selected from any one of the following structures: hydrogen, nitro, cyano, C 1 -C 15 Alkyl, C 1 -C 15 Alkoxy, C 1 -C 15 Alkylthio, -C(=O)-R 16 , halogen-substituted C 1 -C 15 Alkyl, C 1 -C 15 Alkoxy or C 1 -C 15 an alkylthio group;

[0011] M is selected from a single bond or -C(=O)-;

[0012] R 14 Select any one of the following structures: C 1 -C 15 Alkyl, C 1 -C 15 Alkoxy, C 3 -C 15 Cycloalkyl, C 6 -C 15 The aromatic group, C 3 -C 15 Heterocycloalkyl, C 4 -C 15 Heteroaryl, halogen-substituted C 1 -C 15 Alkyl or C 1 -C 15 Alkoxy, substituted C 3 -C 15 Cycloalkyl, C 6 -C 15 The aromatic group, C 3 -C 15 Heterocycloalkyl or C 4 -C 15 heteroaryl;

[0013] R 15 Select any one of the following structures: C 1 -C 15 Alkyl, C 1 -C 15 Alkoxy, C 3 -C 15 Cycloalkyl, C3 -C 15 Heterocycloalkyl, C 4 -C 15 Heteroaryl, C 6 -C 15 Aryl, halogen-substituted C 1 -C 15 Alkyl or C 1 -C 15 Alkoxy, substituted C 3 -C 15 Cycloalkyl, C 6 -C 15 The aromatic group, C 3 -C 15 Heterocycloalkyl or C 4 -C 15 heteroaryl;

[0014] R 16 Select any one of the following structures: C 3 -C 15 Cycloalkyl, C 3 -C 15 Heterocycloalkyl, C 4 -C 15 Heteroaryl, C 6 -C 15 The aryl, substituted C 3 -C 15 Cycloalkyl, C 6 -C 15 The aromatic group, C 3 -C 15 Heterocycloalkyl or C 4 -C 15 The heteroaryl group.

[0015] Furthermore, the R 9 The structure is shown in formula (2):

[0016]

[0017] In formula (2), X is CH and / or N, and the number of X being N is 1 to 3 non-adjacent ones;

[0018] 1-2 hydrogen atoms in formula (2) are nitro, cyano, amine, C 1 -C 8 Alkyl, C 1 -C 8 Alkoxy, C 1 -C 8 Alkylthio, C 1 -C 8 The haloalkyl group, C 3 -C15 Cycloalkyl, C 3 -C 15 Heterocycloalkyl, C 6 -C 12 Aryl, C 4 -C 15 Heteroaryl, and / or substituted C 3 -C 15 Cycloalkyl, C 6 -C 15 The aromatic group, C 3 -C 15 Heterocycloalkyl or C 4 -C 15 The heteroaryl group is substituted.

[0019] Furthermore, R 9 Middle C 3 -C 15 The heterocycloalkyl group is selected from a five-membered ring or a six-membered ring, and contains at least one O or N in the molecule.

[0020] Furthermore, R 9 Middle C 3 -C 15 The heterocycloalkyl group is selected from: morpholinyl and pyranyl.

[0021] Furthermore, R 9 Middle C 1 -C 8 The halogenated alkyl radical is selected from the group consisting of fluorine, chlorine and bromine.

[0022] Furthermore, R 9 Middle C 1 -C 8 The haloalkyl group is selected from the group consisting of fluorine;

[0023] Furthermore, R 9 The structures are: pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, the hydrogen atoms on the pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl can be the same or different cyano, nitro, amino, C 1 -C 4 Alkyl, C 1 -C 4 Fluorinated alkyl, C 1 -C 4 Alkoxy, C 1 -C 4 Alkylthio, C 1 -C 4 It is substituted by alkylsulfone, morpholinyl or pyranyl.

[0024] Furthermore, the C 3 -C 15The heterocycloalkyl group is a five-membered or six-membered ring containing 1-2 of N, O, and S in the molecule;

[0025] Furthermore, C 3 -C 15 The heterocycloalkyl group is pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyridine, piperidine, pyrazine, pyrimidine, pyridazine, morpholine, thimorpholine, piperazine, benzopyrrole, benzofuran, benzothiophene, benzimidazole, benzoxazole, benzothiazole, benzopyridine, benzopiperidine, benzopyrazine, benzopyrimidine, benzopyridazine, benzomorpholine, benzothimorpholine, or benzopiperazine;

[0026] Furthermore, C 3 -C 15 The heterocycloalkyl group is: furan, thiophene, thiazole, benzofuran, benzothiophene;

[0027] Further, C 6 -C 12 The aryl group is phenyl, tolyl, biphenyl or naphthyl.

[0028] The C 3 -C 15 The cycloalkyl group is a structure shown in formula (3):

[0029] In formula (3), the value range of n is 0-5; the value range of m is 1-5;

[0030] Furthermore, the C 4 -C 15 The heteroaryl group is a structure shown in formula (4):

[0031]

[0032] In formula (4), Y is O, S, S(=O) or S(=O) 2 ; The value range of p is 0-5, 0-5 includes 0, 1, 2, 3, 4, 5; R 17 -R 19 Each independently selected from any one of the following structures: hydrogen, C 1 -C 5 Alkyl, C 1 -C 5 or, R 17 and R 18， or R 18 and R 19 Any pair in -C(R 20 )=C(R 21 )-C(R 22 )=C(R 23 )-; where R 20 -R23 Each independently selected from the following structures: hydrogen, C 1 -C 5 Alkyl, C 1 -C 5 of alkoxy.

[0033] Furthermore, the R 16 It is an unsaturated five-membered ring group, an unsaturated six-membered ring group, or a condensed ring group formed by condensing an unsaturated six-membered ring group with an unsaturated five ... 1 -C 5 Alkyl, C 1 -C 5 An unsaturated five-membered ring group, an unsaturated six-membered ring group or a condensed ring group formed by condensing an unsaturated six-membered ring and an unsaturated five-membered ring group, which is substituted with at least one group in the alkoxy group.

[0034] Furthermore, when R 16 It is an unsaturated five-membered heterocyclic group containing 1-2 heteroatoms among N, O and S, and its structure is R 20 -R 22 independently selected from hydrogen, C 1 -C 5 Alkyl, C 1 -C 5 an alkoxy group; or R 20 -R 22 are independently selected from hydrogen;

[0035] Further, unsubstituted or C 1 -C 5 Alkyl, C 1 -C 5 An unsaturated six-membered ring substituted with an alkoxy group, the structure of which is R 23 -R 27 independently selected from hydrogen, C 1 -C 5 Alkyl, C 1 -C 5 Alkoxy, C 3 -C 15 Cycloalkyl, C 1 -C 15 The halogenated alkyl, C 1 -C 15 A haloalkoxy group, wherein C 1 -C 5 Alkyl, C 1 -C 5The alkoxy group is uninterrupted or is interrupted by at least one O; or R 23 -R 27 Middle C 1 -C 15 The halogenated alkyl, C 1 -C 15 The halogen in the halogenated alkoxy group is selected from the group consisting of fluorine, chlorine, and bromine; or R 23 -R 27 Middle C 1 -C 15 The halogenated alkyl, C 1 -C 15 The halogen in the haloalkoxy group is selected from fluorine.

[0036] Furthermore, the substituted C 3 -C 15 Cycloalkyl, C 6 -C 15 The aromatic group, C 3 -C 15 The heterocycloalkyl or C4-C15 heteroaryl is specifically cyano, nitro, C 1 -C 8 Alkyl, C 1 -C 8 Alkoxy, C 1 -C 8 The halogenated alkyl, C 1 -C 8 The haloalkoxy, C 3 -C 15 Cycloalkyl, C 3 -C 15 Heterocycloalkyl, C 1 -C 8 Cycloalkoxy, C 1 -C 8 At least one of the heterocycloalkoxy groups is substituted with C 3 -C 15 Cycloalkyl, C 6 -C 15 The aromatic group, C 3 -C 15 A heterocycloalkyl group or a C4-C15 heteroaryl group, wherein C 1 -C 8 Alkyl, C 1 -C 8 Alkoxy, C 1 -C 8 The halogenated alkyl, C 1 -C 8 The haloalkoxy group is uninterrupted or is interrupted by at least one O.

[0037] Furthermore, the structure of the carbazole photoinitiator is any one of the following:

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046] In a second aspect, a photopolymerizable composition comprises the following components (a) to (b):

[0047] (a) at least one ethylenically unsaturated photopolymerizable compound;

[0048] (b) a photoinitiator, wherein the photoinitiator comprises the carbazole photoinitiator.

[0049] Further, the ethylenically unsaturated photopolymerizable compound is a resin obtained by reacting a saturated or unsaturated polyanhydride, an epoxy resin and an unsaturated monocarboxylic acid. The ethylenically unsaturated photopolymerizable compound has one or more ethylenic double bonds. It has a low molecular weight (monomer type) or a high molecular weight (oligomer type). For example, it includes an alkali-developable resin having a free carboxyl group. The acid value is preferably 50-600 mg KOH / g, more preferably 100-300 mg KOH / g. The acid value described here is the acid value according to DIN EN 12634.

[0050] Furthermore, the photoinitiator further comprises at least one second photoinitiator and / or additives. The additives are, for example, one or more components selected from thermal free radical initiators, pigments, fillers, dispersants and sensitizers.

[0051] Further, the content of the photoinitiator is 0.05-25 wt %; the total solid content of the ethylenically unsaturated photopolymerizable compound (ie the amount of all components without solvent) is 2-98 wt %, more preferably 5-90 wt %, especially 10-80 wt %.

[0052] The advantages of the present invention over similar inventions are:

[0053] (1) The present invention enhances the electron-withdrawing ability of carbazole by introducing a nitrogen-containing heteroaryl group into the carbazole structure. The structural modification causes a redistribution of the electron cloud density inside the molecule, thereby reducing the energy level gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). Since the energy required for the transition from HOMO to LUMO is reduced, the molecule can more easily absorb external energy and undergo electronic excitation, thereby improving the photosensitivity of the molecule. In addition, the reduction in the energy level gap causes the ultraviolet absorption peak to move toward a longer wavelength (i.e., red shift), making the photoinitiator more effective in absorbing light of a specific wavelength, thereby making it more suitable for excitation of LED light sources;

[0054] (2) The present invention can provide electrons through the nitrogen-containing heterocycle to stabilize free radical intermediates and reduce the formation of colored byproducts caused by photodegradation, thereby improving the stability of the photoinitiator. The larger nitrogen-containing heterocycle provides additional steric protection to prevent non-radiative transitions and aggregation between molecules, reduce the occurrence of photooxidation reactions, and further reduce the occurrence of yellowing. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0056] Figure 1 This is the NMR image of Example 1 in the present invention. DETAILED DESCRIPTION

[0057] The embodiments of the present invention will be clearly and completely described below in conjunction with the examples, and the described examples are only some examples of the present invention, rather than all examples. The following description of at least one exemplary embodiment is actually only illustrative and is by no means intended to limit the present invention and its application or use. Based on the examples in the present invention, all other examples obtained by ordinary technicians in the field without creative work are within the scope of protection of the present invention.

[0058] The reagents or instruments used in the present invention, if the manufacturer is not specified, are all conventional products that can be purchased from the market. For process parameters not specifically specified, conventional techniques can be used.

[0059] Embodiment 1:

[0060] The synthesis steps of the compound involved in this embodiment are as follows:

[0061]

[0062] Step 1: In a round-bottom flask, add 9H-carbazole (20 g, 1 eq), 2-chloro-4,6-dimethoxy-1,3,5-triazine (21 g, 1 eq), Pd 2 (DBA) 3 (0.1 g, 0.001 eq), triphenylphosphine (6.27 g, 0.2 eq), sodium tert-butoxide (22.99 g, 2 eq), and 200 ml of toluene were added and reacted at 100°C for 8-12 h. When the reaction was completed, it was extracted with water and 200 ml of dichloromethane, the aqueous phase was washed 2-3 times with 50 ml of dichloromethane, the organic layers were combined, and MgSO 4 Dry, spin dry, add 100 ml of ethanol, stir, heat and reflux for 1 h, pass through silica gel cake while hot, spin dry the filtrate to obtain intermediate 1 (28.51 g);

[0063] Step 2: In a round-bottom flask, add intermediate 1 (28.51 g, 1 eq) and aluminum chloride (24.82 g, 2 eq) to 300 ml of dichloromethane, slowly dropwise add propionyl chloride (10.33 g, 1.2 eq) dissolved in 50 mL of dichloromethane solution under an ice-water bath, react at room temperature for 6-8 h, and when the reaction is complete, add 100 ml of 0.2 mol / L HCl at 0°C, stir, let stand, retain the organic phase, wash the aqueous phase with dichloromethane 2-3 times, combine the organic phases, adjust the pH of the system to neutral with a dilute sodium bicarbonate aqueous solution, retain the organic phase, pass through a silica gel cake, and spin dry to obtain intermediate 2 (27.31 g);

[0064] Step 3: In a round-bottom flask, add intermediate 2 (27.31 g, 1 eq) to 300 ml of DMF, slowly drop concentrated hydrochloric acid (3.82 g, 0.5 eq) and isobutyl nitrite (11.66 g, 1.5 eq) in sequence, and react at room temperature with stirring for 3-5 h. After the reaction is completed, add 1000 ml of water, stir, let stand, retain the organic phase, wash the aqueous phase with 100 ml of n-heptane 1-2 times, combine the organic phases, add 300 ml of water, stir, adjust the pH to neutral with 0.5 mol / L sodium bicarbonate, retain the organic phase, spin dry, add ethanol and reflux for 1 h, filter while hot, spin dry, and dry to obtain intermediate 3 (25.41 g);

[0065] Step 4: In a round-bottom flask, add intermediate 3 (25.41 g, 1 eq) and triethylamine (7.91 g, 2 eq) to 300 mL of dichloromethane, slowly dropwise add acetyl chloride (10.22 g, 1.2 eq) dissolved in 50 mL of dichloromethane solution under an ice bath, react for 4-6 hours, confirm that the reaction is complete, add 500 ml of water at 0°C and stir for 1 hour, then let stand to separate and retain the organic phase, adjust the pH of the organic phase to neutral with 0.1 mol / L dilute hydrochloric acid, wash once and retain the organic phase again, dry with 30 g of anhydrous magnesium sulfate, and spin into a viscous liquid; dissolve the viscous liquid in 100 ml of ethanol, heat to reflux for 1 h, cool to room temperature, and a white solid product can be precipitated. The final product is obtained by filtering and drying, and 22.25 g of the final product is obtained.

[0066] 1 H NMR(CDCL3): δ8.69-8.64(m,1H),8.38-8.28(m,1H),8.10(dd,1H),7.89-7.82(m, 1H),7.81-7.72(m,1H),7.42-7.30(m,2H),3.96(s,6H),2.44(s,3H),2.17(s,3H).

[0067] MS (m / z): 433 (M+1).

[0068] Example 2: Synthesis of Compound 5

[0069] Compound 5 was synthesized by the method of reference example 1. 1 H NMR(CDCL3): δ8.70-8.66(m,1H),8.38-8.28(m,1H),8.08(dd,1H),7.93-7.86(m,2H),7.83- 7.73(m,1H),7.61(dd,1H),7.42-7.30(m,2H),7.27-7.19(m,1H),2.57(s,6H),2.17(s,3H).

[0070] MS (m / z): 534 (M+1).

[0071] Example 3: Synthesis of Compound 16

[0072] Compound 16 was synthesized by the method of Example 1. 1H NMR(CDCL3): δ8.73-8.68(m,1H),8.38-8.28(m,1H),8.08(dd,1H),7.77-7.64(m,4 H),7.42-7.30(m,2H),7.17-7.09(m,2H),4.49(m,2H),2.17(s,3H),1.44(s,18H).

[0073] MS (m / z): 696 (M+1).

[0074] Example 4: Synthesis of Compound 20

[0075] Compound 20 was synthesized by the method of Example 1. 1 H NMR (CDCL3): δ8.69-8.64(m,1H),8.36-8.29(m,1H),8.10(dd,1H),7.91-7.84(m,1H),7.84-7.77(m,1H),7.42-

[0076] 7.30(m,2H),3.86-3.68(m,16H),2.44(s,4H),1.93-1.79(m,2H),1.66-1.50(m,2H),1.45(m,6H).

[0077] MS (m / z): 612 (M+1).

[0078] Example 5: Synthesis of Compound 26

[0079] Compound 26 was synthesized by the method of Reference Example 1. 1 H NMR(CDCL3): δ8.62(dd,1H),8.34-8.25(m,1H),8.08(dd,1H),8.01-7.97(m,1H),7.90-7.83(m,1H),7.74-7.65(m,1H),7.40-7.30(m,2H),4. 08-3.96(m,2H),3.75(dd,1H),2.94(m,1H),2.81(m,1H),2.45(d,3H), 2.39(s,3H),2.21-2.09(m,4H),1.92(m,1H),1.43(s,3H),1.32(s,3H).

[0080] MS (m / z): 515 (M+1).

[0081] Example 6: Synthesis of Compound 32

[0082] Compound 32 was synthesized by the method of Reference Example 1. 1H NMR(CDCL3): δ8.76(d,1H),8.70(d,1H),8.36-8.26(m,2H),8.07(dd,1H),7.91-7.81(m,2H),7.83-7.78(m, 1H),7.81-7.73(m,1H),7.56-7.49(m,2H),7.49-7.41(m,1H),7.41-7.30(m,2H),7.24(t,1H),2.17(s,3H).

[0083] MS (m / z): 435 (M+1).

[0084] Example 7: Synthesis of Compound 42

[0085] Compound 42 was synthesized by the method of Example 1. 1H NMR (CDCL3): δ8.68 (d, 1H), 8.37-8.27 (m, 2H), 8.12-7.99 (m, 2H), 7.90-7.82 (m, 2H), 7.82-7.72 (m, 2H), 7.48-7.34 (m, 1H), 7.38-7.30 (m, 3H), 6.57 (d, 1H), 3.07 (s, 6H), 2.17 (s, 3H).

[0086] MS (m / z): 534 (M+1).

[0087] Example 8: Synthesis of Compound 9

[0088] Compound 9 was synthesized by the method of Reference Example 1. 1 H NMR(CDCL3): δ8.69-8.64(m,1H),8.38-8.28(m,1H),8.10(dd,1H),7.92-7.85(m,1H),7.84-7.76(m,1 H),7.42-7.30(m,2H),3.27(s,12H),2.82(q,2H),2.49(t,2H),1.68(m,2H),1.22(t,3H),0.93(t,3H).

[0089] MS (m / z): 502 (M+1).

[0090] Example 9: Synthesis of Compound 50

[0091] Compound 50 was synthesized by the method of Example 1. 1H NMR(CDCL3): δ8.67(d,1H),8.36(dd,1H),8.31-8.22(m,1H),8.10-7.98(m,2H),7.9 4-7.86(m,1H),7.79(d,1H),7.71-7.63(m,1H),7.39-7.30(m,2H),7.25(m,1H),4.92 (m,1H),2.38(m,1H),1.81-1.65(m,4H),1.60-1.45(m,4H),1.50-1.40(m,2H),1.44- 1.35(m,1H),1.39-1.31(m,2H),1.36-1.27(m,1H),1.32-1.18(m,2H),0.91(m,12H).

[0092] MS (m / z): 556 (M+1).

[0093] Example 10: Synthesis of Compound 14

[0094] Compound 14 was synthesized by the method of Reference Example 1. 1 H NMR(CDCL3): δ8.74(d,2H),8.38-8.28(m,2H),8.18-8.08(m,1H),7.95-7.88(m,1H),7.86-7.7 6(m,1H),7.72-7.64(m,1H),7.64-7.54(m,2H),7.42-7.30(m,2H),3.27(s,12H),2.17(s,3H).

[0095] MS (m / z): 650 (M+1).

[0096] Embodiment 11:

[0097] The synthesis steps of the compound involved in this embodiment are as follows:

[0098]

[0099] Step 1: In a round-bottom flask, add 9H-carbazole (20 g, 1 eq), 2-chloro-4,6-dimethoxy-1,3,5-triazine (21 g, 1 eq), Pd 2 (DBA) 3 (0.1 g, 0.001 eq), triphenylphosphine (6.27 g, 0.2 eq), sodium tert-butoxide (22.99 g, 2 eq), and 200 ml of toluene were added and reacted at 100°C for 8-12 h. When the reaction was completed, it was extracted with water and 200 ml of dichloromethane, the aqueous phase was washed 2-3 times with 50 ml of dichloromethane, the organic layers were combined, and MgSO 4Dry, spin dry, add 100 ml of ethanol, stir, heat and reflux for 1 h, pass through silica gel cake while hot, spin dry the filtrate to obtain intermediate 1 (27.99 g);

[0100] Step 2: In a round-bottom flask, add intermediate 1 (27.99 g, 1 eq) and aluminum chloride (24.37 g, 2 eq) to 300 ml of dichloromethane, slowly dropwise add 4-(2,2-dimethyl-1,3-dioxolan-4-yl)methoxy)-2-methylbenzoyl chloride (31.22 g, 1.2 eq) dissolved in 100 mL of dichloromethane solution under an ice-water bath, react at room temperature for 6-8 h, lower the system temperature to 0 degrees Celsius, slowly dropwise add 2-propoxyacetyl chloride (14.98 g, 1.2 eq) dissolved in 100 mL of dichloromethane solution, react at room temperature for 6-8 h, and when the reaction is complete, add 0.2 mol / L HCl at 0°C. 100ml, stirred, let stand, retain the organic phase, wash the aqueous phase with dichloromethane 2-3 times, combine the organic phases, adjust the pH of the system to neutral with dilute sodium bicarbonate aqueous solution, retain the organic phase, pass through a silica gel cake, and spin dry to obtain intermediate 2 (45.21g);

[0101] Step 3: In a round-bottom flask, add intermediate 2 (45.21 g, 1 eq) to 400 ml of DMF, slowly drop concentrated hydrochloric acid (3.50 g, 0.5 eq) and isobutyl nitrite (10.68 g, 1.5 eq) in sequence, and react at room temperature with stirring for 3-5 h. After the reaction is completed, add 1000 ml of water, stir, stand, retain the organic phase, wash the aqueous phase with 100 ml of n-heptane 1-2 times, combine the organic phases, add 300 ml of water, stir, adjust the pH to neutral with 0.5 mol / L sodium bicarbonate, retain the organic phase, spin dry, add ethanol and reflux for 1 h, filter while hot, spin dry, and dry to obtain intermediate 3 (41.20 g);

[0102] Step 4: In a round-bottom flask, add intermediate 3 (25.41g, 1eq) and triethylamine (12.23g, 2eq) to 300mL of dichloromethane, slowly drop acetyl chloride (10.63g, 1.2eq) dissolved in 50mL of dichloromethane solution under an ice bath, react for 4-6 hours, confirm that the reaction is complete, add 500ml of water at 0°C and stir for 1 hour, then let stand to separate and retain the organic phase, adjust the pH of the organic phase to neutral with 0.1mol / L dilute hydrochloric acid, wash once and retain the organic phase again, dry with 30g of anhydrous magnesium sulfate, and spin into a viscous liquid; dissolve the viscous liquid in 100ml of ethanol, heat to reflux for 1h, cool to room temperature, and a white solid product can be precipitated. The final product is obtained by filtering and drying, and 38.66g of the final product is obtained.

[0103] 1H NMR(CDCL3): δ8.81-8.77(m,1H),8.72(d,1H),8.13-8.03(m,2H),7.92-7.85(m,1H),7.82(dd,1H),7.66(d,1H),6.90(dd,1H),6.85(d,1H),4.34-

[0104] 4.17(m,4H),4.09 -3.96(s,8H),3.73(dd,1H),2.60-2.48(m,1H),2.42(d,3H),1.93-1.80(m,1H),1.84-1. 72(m,1H),1.76-1.68(m,2H),1.66-1.39(m,8H),1.40(s,3H),1.34(s,3H),0.98(t,3H).

[0105] MS (m / z): 794 (M+1).

[0106] Example 12: Synthesis of Compound 56

[0107] Compound 56 was synthesized by the method of Reference Example 11. 1 H NMR (CDCL3): δ8.82-8.77(m,1H),8.50(d,1H),8.16-8.06(m,2H),7.95-7.88(m,1H),7.86-7.78(m,3H),7.60-7.45(m,3H),3.27 -3.19(m,13H),2.57(q,2H),1.80-1.61(m,2H),1.55-1.21(m,6H),1.17(t,3H),0.97-0.84(m,6H).

[0108] MS (m / z): 662 (M+1).

[0109] Example 13: Synthesis of Compound 59

[0110] Compound 59 was synthesized by the method of Reference Example 11. 1H NMR(CDCL3): δ8.78(d,1H),8.69(d,1H),8.35(d,1H),8.10(dd,1H),8.02(d,1H),7.90(d,1H),7.87-7.77(m,2H),7.66(d,1H),6.93-6.8 2(m,2H),4.30(dd,1H),4.21(p,1H),4.01(m,2H),3.73(dd,1H),3.20(s,6H),2.47-2.40(m,6H),2.17(s,3H),1.40(s,3H),1.34(s,3H).

[0111] MS (m / z): 664 (M+1).

[0112] Example 14: Synthesis of Compound 61

[0113] Compound 61 was synthesized by the method of Reference Example 11. 1 H NMR(CDCL3): δ8.70(d,1H),8.38-8.28(m,1H),8.07(dd,1H),7.77-7.66(m,2H),7.59(d,1H),7.36(m,2H),6.97(s,1H),7.0 0-6.92(m,1H),4.54(m,1H),3.62(dd,1H),3.40(dd,1H),3.37(s,3H),2.45(s,3H),2.17(s,3H),1.44(s,18H),1.33(d,3H).

[0114] MS (m / z): 542 (M+1).

[0115] Example 15: Synthesis of Compound 66

[0116] Compound 66 was synthesized by the method of Reference Example 11. 1 H NMR(CDCL3): δ8.99(s,1H),8.65(d,1H),8.08(dd,1H),7.91(d,3H),7.87-7.81(m, 1H),3.87(s,3H),2.82(q,2H),2.56(s,3H),2.46(s,3H),2.17(s,3H),1.22(t,3H).

[0117] MS (m / z): 505 (M+1).

[0118] Example 16: Synthesis of Compound 69

[0119] Compound 69 was synthesized by the method of Reference Example 11. 1H NMR(CDCL3): δ8.81(s,1H),8.70(dd,1H),8.66-8.60(m,1H),8.36-8.29(m,1H),8.28-8.17(m ,2H),8.02(dd,1H),7.66(d,1H),7.53(m,1H),7.38-7.29(m,1H),7.01(s,2H),6.94(dd,1H), 6.87(d,1H),6.81(d,1H),4.30(dd,1H),4.21(p,1H),4.01(m,2H),3.91(s,3H),3.85(s,3H), 3.73(dd,1H),2.42(s,3H),2.36(s,6H),2.29(s,3H),2.17(s,3H),1.40(s,3H),1.34(s,3H).

[0120] MS (m / z): 834 (M+1).

[0121] Embodiment 17:

[0122] The synthesis steps of the compound involved in this embodiment are as follows:

[0123]

[0124] Step 1: In a round-bottom flask, add 9H-carbazole (20 g, 1 eq), 2-chloro-3,4-dimethoxypyridine (20.76 g, 1 eq), Pd 2 (DBA) 3 (0.1 g, 0.001 eq), triphenylphosphine (6.27 g, 0.2 eq), sodium tert-butoxide (22.99 g, 2 eq), and 200 ml of toluene were added and reacted at 100°C for 8-12 h. When the reaction was completed, it was extracted with water and 200 ml of dichloromethane, the aqueous phase was washed 2-3 times with 50 ml of dichloromethane, the organic layers were combined, and MgSO 4 Dry, spin dry, add 100 ml of ethanol, stir, heat and reflux for 1 h, pass through silica gel cake while hot, spin dry the filtrate to obtain intermediate 1 (28.56 g);

[0125] Step 2: In a round-bottom flask, add intermediate 1 (28.56 g, 1 eq) and aluminum chloride (25.02 g, 2 eq) to 300 ml of dichloromethane, slowly dropwise add 3-methylbenzoyl chloride (17.41 g, 1.2 eq) dissolved in 100 mL of dichloromethane solution under an ice-water bath, react at room temperature for 6-8 h, lower the system temperature to 0 degrees Celsius, slowly dropwise add 2-ethylhexanoyl chloride (18.32 g, 1.2 eq) dissolved in 100 mL of dichloromethane solution, react at room temperature for 6-8 h, and when the reaction is complete, add 100 ml of 0.2 mol / L HCl at 0°C, stir, stand, retain the organic phase, wash the aqueous phase with dichloromethane 2-3 times, combine the organic phases, adjust the system pH to neutral with a dilute sodium bicarbonate aqueous solution, retain the organic phase, pass through a silica gel cake, and spin dry to obtain intermediate 2 (38.98 g);

[0126] Step 3: In a round-bottom flask, add intermediate 2 (38.98 g, 1.0 eq), hydroxylamine hydrochloride (7.59, 1.5 eq), sodium acetate (8.97 g, 1.5 eq) to 200 g of tetrahydrofuran, react for 6-12 h, and after the reaction is complete by TLC detection, add the reaction solution to 1000 ml of water, keep at 0 ° C overnight, filter to obtain a powdery solid, dissolve the powdery solid in 100 ml of THF, add 20 g of anhydrous magnesium sulfate to dry, filter, rotary evaporate, and dry to obtain intermediate 3 (35.62 g);

[0127] Step 4: In a round-bottom flask, add intermediate 3 (25.41g, 1eq) and triethylamine (12.79g, 2eq) to 300mL of dichloromethane, slowly drop acetyl chloride (5.95g, 1.2eq) dissolved in 50mL of dichloromethane solution under an ice bath, react for 4-6 hours, confirm that the reaction is complete, add 500ml of water at 0°C and stir for 1 hour, then let stand to separate and retain the organic phase, adjust the pH of the organic phase to neutral with 0.1mol / L dilute hydrochloric acid, wash once and retain the organic phase again, dry with 30g of anhydrous magnesium sulfate, and spin into a viscous liquid; dissolve the viscous liquid in 100ml of ethanol, heat to reflux for 1h, cool to room temperature, and a white solid product can be precipitated. The final product is obtained by filtering and drying, and 29.88g of the final product is obtained.

[0128] 1H NMR(CDCL3): δ8.75(d,1H),8.58(d,1H),8.24(d,1H),8.08(d,1H),7.81-7.61(m,5H),7.39(t,1H),7.28-7.22(m,1H),6.81(d, 1H),3.91(s,3H),3.85(s,3H),2.95(m,1H),2.36(s,3H),2.20(s,3H),1.79-1.60(m,2H),1.55-1.23(m,6H),0.98-0.82(m,6H).

[0129] MS (m / z): 606 (M+1).

[0130] Example 18: Synthesis of Compound 60

[0131] Compound 60 was synthesized by the method of Reference Example 17. 1 H NMR(CDCL3): δ9.02(d,1H),8.74-8.69(m,1H),8.46(d,1H),8.35(d,1H),7.92-7.73(m,5H),7.65(dd,1H),3.20(s,6H),2.17(s,3H),1.23(s,9H).

[0132] MS (m / z): 541 (M+1).

[0133] Example 19: Synthesis of Compound 72

[0134] Compound 72 was synthesized by the method of Reference Example 17. 1 H NMR(CDCL3): δ9.05(s,2H),8.72(d,1H),8.34(d,1H),8.02-7.96(m,1H),7.82-7.71(m,3 H),2.84(q,3H),2.05-1.89(m,2H),1.84-1.68(m,3H),1.72-1.56(m,3H),1.21(d,12H).

[0135] MS (m / z): 522 (M+1).

[0136] Example 20: Synthesis of Compound 83

[0137] Compound 83 was synthesized by the method of Reference Example 17. 1H NMR(CDCL3): δ8.78(s,1H),8.67-8.54(m,3H),8.50-8.45(m,1H),8.31-8.25(m,1H),8.07-8.00(m,1 H),7.94-7.83(m,3H),7.78-7.69(m,2H),7.53(td,1H),7.48-7.31(m,3H),3.95(s,3H),2.20(s,3H).

[0138] MS (m / z): 615 (M+1).

[0139] Embodiment 21:

[0140] The synthesis steps of the compound involved in this embodiment are as follows:

[0141]

[0142] Step 1: In a round-bottom flask, add 5-nitro-11H-benzo[a]carbazole (20 g, 1 eq), 2-chloro-4,6-dimethoxy-1,3,5-triazine (13.39 g, 1 eq), Pd 2 (DBA) 3 (0.1 g, 0.06 eq), triphenylphosphine (4 g, 0.2 eq), sodium tert-butoxide (14.66 g, 2 eq), and 200 ml of toluene were added and reacted at 100 °C for 8-12 h. When the reaction was completed, it was extracted with water and 200 ml of dichloromethane, and the aqueous phase was washed 2-3 times with 50 ml of dichloromethane. The organic layers were combined and washed with MgSO 4 Dry, spin dry, add 100 ml of ethanol, stir, heat and reflux for 1 h, pass through silica gel cake while hot, spin dry the filtrate to obtain intermediate 1 (23.84 g);

[0143] Step 2: In a round-bottom flask, add intermediate 1 (23.84 g, 1 eq) and aluminum chloride (15.84 g, 2 eq) to 300 ml of dichloromethane, slowly dropwise add acetyl chloride (5.59 g, 1.2 eq) dissolved in 100 mL of dichloromethane solution under an ice-water bath, react at room temperature for 6-8 h, and when the reaction is complete, add 100 ml of 0.2 mol / L HCl at 0°C, stir, let stand, retain the organic phase, wash the aqueous phase with dichloromethane 2-3 times, combine the organic phases, adjust the system pH to neutral with dilute sodium bicarbonate aqueous solution, retain the organic phase, pass through a silica gel cake, and spin dry to obtain intermediate 2 (21.8 g);

[0144] Step 3: In a round-bottom flask, add intermediate 2 (21.8 g, 1.0 eq), hydroxylamine hydrochloride (5.12, 1.5 eq), sodium acetate (6.05 g, 1.5 eq) to 200 g of tetrahydrofuran, react for 6-12 h, and after the reaction is complete by TLC, add the reaction solution to 1000 ml of water, keep at 0 ° C overnight, filter to obtain a powdery solid, dissolve the powdery solid in 100 ml of THF, add 20 g of anhydrous magnesium sulfate to dry, filter, rotary evaporate, and dry to obtain intermediate 3 (19.38 g);

[0145] Step 4: In a round-bottom flask, add intermediate 3 (19.38 g, 1 eq) and triethylamine (8.56 g, 2 eq) to 300 mL of dichloromethane, slowly drop acetyl chloride (3.98 g, 1.2 eq) dissolved in 50 mL of dichloromethane solution under an ice bath, react for 4-6 hours, confirm that the reaction is complete, add 500 ml of water at 0°C and stir for 1 hour, then let stand to separate and retain the organic phase, adjust the pH of the organic phase to neutral with 0.1 mol / L dilute hydrochloric acid, wash once and retain the organic phase again, dry with 30 g of anhydrous magnesium sulfate, and spin into a viscous liquid; dissolve the viscous liquid in 100 ml of ethanol, heat to reflux for 1 h, cool to room temperature, and a white solid product can be precipitated. The final product is obtained by filtering and drying, and 16.22 g of the final product is obtained.

[0146] 1 H NMR(CDCL3): δ9.18(s,1H),8.79-8.72(m,1H),8.60-8.52(m,2H),7.79-7.69( m,2H),7.59(m,1H),7.41-7.32(m,1H),3.96(s,6H),2.45(s,3H),2.20(s,3H).

[0147] MS (m / z): 606 (M+1).

[0148] Example 22: Synthesis of Compound 104

[0149] Compound 104 was synthesized by the method of Reference Example 21. 1 H NMR (CDCL3): δ9.34(s,1H),9.29(d,1H),8.37-8.27(m,2H),8.19(d,1H),7.77-7.67(m,2H),4.00(s,3H),2.45(s,3H),2.20(s,3H).

[0150] MS (m / z): 445 (M+1).

[0151] Example 23: Synthesis of Compound 111

[0152] Compound 111 was synthesized by the method of Example 21. 1 H NMR(CDCL3): δ8.71(d,1H),8.57(d,1H),8.41(dd,2H),8.15(d,1H),8.12-8.05(m, 1H),7.68(m,2H),7.48(m,5H),3.88-3.77(m,4H),2.06-1.96(m,4H),1.24(s,9H).

[0153] MS(m / z):543(M+1).

[0154] Embodiment 24:

[0155] The synthesis steps of the compound involved in this embodiment are as follows:

[0156]

[0157] Step 1: In a round-bottom flask, add 5-nitro-11H-benzo[a]carbazole (20 g, 1 eq), 2-chloro-3-methyl-4-nitropyridine (15.89 g, 1 eq), Pd 2 (DBA) 3 (0.1 g, 0.08 eq), triphenylphosphine (4.83 g, 0.2 eq), sodium tert-butoxide (17.96 g, 2 eq), and 200 ml of toluene were added and reacted at 100 °C for 8-12 h. When the reaction was completed, it was extracted with water and 200 ml of dichloromethane, and the aqueous phase was washed 2-3 times with 50 ml of dichloromethane. The organic layers were combined and washed with MgSO 4 Dry, spin dry, add 100 ml of ethanol, stir, heat and reflux for 1 h, pass through silica gel cake while hot, spin dry the filtrate to obtain intermediate 1 (25.65 g);

[0158] Step 2: In a round-bottom flask, add intermediate 1 (23.84 g, 1 eq) and aluminum chloride (29.03 g, 3 eq) to 300 ml of dichloromethane, slowly dropwise add acetyl chloride (12.53 g, 2.2 eq) dissolved in 100 mL of dichloromethane solution under an ice-water bath, react at room temperature for 6-8 h, and when the reaction is complete, add 100 ml of 0.2 mol / L HCl at 0°C, stir, let stand, retain the organic phase, wash the aqueous phase with dichloromethane 2-3 times, combine the organic phases, adjust the pH of the system to neutral with a dilute sodium bicarbonate aqueous solution, retain the organic phase, pass through a silica gel cake, and spin dry to obtain intermediate 2 (22.68 g);

[0159] Step 3: In a round-bottom flask, add intermediate 2 (22.68 g, 1.0 eq), hydroxylamine hydrochloride (10.81 g, 3 eq), and sodium acetate (12.76 g, 3 eq) to 200 g of tetrahydrofuran and react for 6-12 h. After the reaction is complete as detected by TLC, add the reaction solution to 1000 ml of water, keep at 0°C overnight, and filter to obtain a powdery solid. Dissolve the powdery solid in 100 ml of THF, add 20 g of anhydrous magnesium sulfate to dry, filter, rotary evaporate, and dry to obtain intermediate 3 (18.31 g);

[0160] Step 4: In a round-bottom flask, add intermediate 3 (18.31 g, 1 eq) and triethylamine (11.89 g, 4 eq) to 300 mL of dichloromethane, slowly drop acetyl chloride (6.76 g, 2.2 eq) dissolved in 50 mL of dichloromethane solution under an ice bath, react for 4-6 hours, confirm that the reaction is complete, add 500 ml of water at 0°C and stir for 1 hour, then let stand to separate and retain the organic phase, adjust the pH of the organic phase to neutral with 0.1 mol / L dilute hydrochloric acid, wash once and retain the organic phase again, dry with 30 g of anhydrous magnesium sulfate, and spin into a viscous liquid; dissolve the viscous liquid in 100 ml of ethanol, heat to reflux for 1 h, cool to room temperature, and a white solid product can be precipitated. The final product is obtained by filtering and drying, and 15.77 g of the final product is obtained.

[0161] 1 H NMR(CDCL3): δ8.62(s,1H),8.49(d,1H),8.41-8.35(m,1H),8.33-8.28(m,1H),8.21-8.14(m,1H),7.94(d,1 H),7.80-7.74(m,1H),7.68(dd,1H),7.53(m,1H),7.38-7.29(m,1H),2.44(d,6H),2.30(s,3H),2.18(d,6H).

[0162] MS(m / z):553(M+1).

[0163] Embodiment 25:

[0164] The synthesis steps of the compound involved in this embodiment are as follows:

[0165]

[0166] Step 1: In a round-bottom flask, add 5-nitro-11H-benzo[a]carbazole (20 g, 1 eq), 2-chloropyridine (11.82 g, 1 eq), Pd 2 (DBA) 3(0.08g, 0.001eq), triphenylphosphine (4.78g, 0.2eq), sodium tert-butoxide (17.53g, 2eq), toluene 200ml, react at 100°C for 8-12h. After the reaction is completed, extract with water and 200ml dichloromethane, wash the aqueous phase with 50ml dichloromethane 2-3 times, combine the organic layers, dry with MgSO4, spin dry, add 100ml ethanol, stir, heat and reflux for 1h, pass through silica gel cake while hot, spin dry the filtrate to obtain intermediate 1 (21.58g);

[0167] Step 2: In a round-bottom flask, add intermediate 1 (21.58 g, 1 eq) and aluminum chloride (29.13 g, 3 eq) to 300 ml of dichloromethane, slowly dropwise add 3-ethylheptanoyl chloride (28.30 g, 2.2 eq) dissolved in 100 mL of dichloromethane solution under an ice-water bath, react at room temperature for 6-8 h, and when the reaction is complete, add 100 ml of 0.2 mol / L HCl at 0°C, stir, let stand, retain the organic phase, wash the aqueous phase with dichloromethane 2-3 times, combine the organic phases, adjust the system pH to neutral with dilute sodium bicarbonate aqueous solution, retain the organic phase, pass through a silica gel cake, and spin dry to obtain intermediate 2 (31.28 g);

[0168] Step 3: In a round-bottom flask, add intermediate 2 (31.28 g, 1 eq) to 300 ml of DMF, slowly drop concentrated hydrochloric acid (5.51 g, 1 eq) and isobutyl nitrite (16.83 g, 3 eq) in sequence, and react at room temperature with stirring for 3-5 h. After the reaction is completed, add 1000 ml of water, stir, let stand, retain the organic phase, wash the aqueous phase with 100 ml of n-heptane 1-2 times, combine the organic phases, add 300 ml of water, stir, adjust the pH to neutral with 0.5 mol / L sodium bicarbonate, retain the organic phase, spin dry, add ethanol and reflux for 1 h, filter while hot, spin dry, and dry to obtain intermediate 3 (25.61 g);

[0169] Step 4: In a round-bottom flask, add intermediate 3 (25.61g, 1eq) and triethylamine (16.42g, 4eq) to 300mL of dichloromethane, slowly drop acetyl chloride (7.01g, 2.2eq) dissolved in 50mL of dichloromethane solution under an ice bath, react for 4-6 hours, confirm that the reaction is complete, add 500ml of water at 0°C and stir for 1 hour, then let stand to separate and retain the organic phase, adjust the pH of the organic phase to neutral with 0.1mol / L dilute hydrochloric acid, wash once and retain the organic phase again, dry with 30g of anhydrous magnesium sulfate, and swirl into a viscous liquid; dissolve the viscous liquid in 100ml of ethanol, heat to reflux for 1h, cool to room temperature, and a white solid product can be precipitated. The final product is obtained by filtering and drying, and 23.74g of the final product is obtained.

[0170] 1 H NMR(CDCL3): δ8.81(s,1H),8.61-8.54(m,1H),8.53-8.48(m,1H),8.41-8.34(m,2H),8.09(m,2H),7.96-7.86(m,2H),7.53(m ,1H),7.38-7.29(m,1H),7.25(m,1H),3.26(m,2H),2.17(s,6H),1.80-1.61(m,4H),1.56-1.21(m,12H),0.97-0.84(m,12H).

[0171] MS(m / z):717(M+1).

[0172] Comparative Example 1

[0173] The compound of Comparative Example 1 is:

[0174] Comparative Example 2

[0175] The compound of Comparative Example 2 is:

[0176] Comparative Example 3

[0177] The compound of Comparative Example 3 is:

[0178] Test example

[0179] The following physical property evaluations were performed on the compounds obtained in the above synthesis examples. In addition, for comparison, the physical property evaluations were also performed on the photopolymerization initiators of the following Comparative Examples 1 to 3. The results are shown in Table 1.

[0180] 1. Maximum absorption wavelength and molar absorption coefficient

[0181] The photoinitiator of the present invention is prepared as 10 -5 mol / L propylene glycol methyl ether acetate (PMA) solution, test its UV-visible absorption spectrum to obtain its maximum absorption wavelength (λ max ), and calculate the molar absorptivity (ε) at the maximum absorption wavelength according to Beer's law max )

[0182] 2. Solubility

[0183] Taking propylene glycol methyl ether acetate (PMA), a reactive diluent widely used in the art, as an example, the maximum weight that can be dissolved in 100 g of solvent at 25° C. is used as the evaluation standard for the photoinitiator of the present invention.

[0184] 3.Light sensitivity

[0185] 20wt% of bisphenol fluorene resin, 0.5wt% of the compound of the present invention as a photopolymerization initiator, 0.1wt% FC-430 (3M leveling agent), and 19.4wt% PMA were placed in a reaction mixing tank with a UV protective cover and a stirrer, and stirred at room temperature to prepare a photopolymerizable composition. The photopolymerizable composition was spin-coated on a glass substrate and dried on a hot plate at 100°C for 1 minute, then exposed using a step mask and developed in a 0.04% KOH aqueous solution. The sensitivity was evaluated based on an exposure dose in which the thickness of the step mask pattern was maintained at 80% of the initial thickness, and the exposure dose in which the thickness of the pattern of comparative example 1 was maintained at 80% of the initial thickness was defined as 1. Other photoinitiators were evaluated. Under the same residual thickness, the exposure dose was small and the sensitivity was high. The results are shown in Table 1.

[0186] Table 1

[0187]

[0188]

[0189] As can be seen from Table 1, the photoinitiator of the present invention has excellent solubility and can be more easily dispersed in various solvents, thereby ensuring uniform distribution of the material during the photopolymerization process. This uniformity is crucial to the performance and appearance of the final product.

[0190] The photoinitiator in the present invention can more efficiently utilize light energy to drive the polymerization reaction, significantly improving the efficiency and production capacity of photocuring. Since the photoinitiator has higher photosensitivity, it can absorb light more effectively and quickly enter the excited state. The photoinitiator in the present invention has a lower energy threshold and can effectively start the polymerization process even under low-intensity light conditions. Therefore, this photoinitiator not only improves production efficiency, but also enhances the applicability and flexibility of the product.

[0191] In addition, the stable performance of the photoinitiator in the present invention under different wavelengths and intensities of light also makes it an ideal choice for a variety of industrial applications, such as printing, coating, 3D printing, and electronic packaging. In short, by using the photoinitiator of the present invention, higher quality product output can be achieved, while meeting the growing demand for photocuring technology in different industries.

[0192] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. A carbazole photoinitiator, characterized in that: The carbazole photoinitiator is a compound having a structure shown in formula (1): In formula (1), R1-R8 are independently selected from hydrogen; or any two adjacent substituents in R1-R8 are -C(R 10 )=C(R 11 )-C(R 12 )=C(R 13 )-; or R3, R6 are independently selected from any one of the following structures: nitro, cyano, C1-C 15 Alkyl, C1-C 15 Alkoxy, C1-C 15 Alkylthio, C1-C 15 Alkyl ester, C3-C 15 Cycloalkyl, C3-C 15 Heterocycloalkyl, C6-C 15 Aryl, C4-C 15 Heteroaryl, -MC(R 14 )=NOC(=O)-R 15 , -C(=O)-R 16 , halogen-substituted C1-C 15 Alkyl, C1-C 15 Alkoxy, C1-C 15 Alkylthio or C1-C 15 Alkyl ester, substituted C3-C 15 Cycloalkyl, C6-C 15 Aryl, C3-C 15 Heterocycloalkyl or C4-C 15 and at least one of R3 and R6 is -MC(R 14 )=NOC(=O)-R 15 ; R9 is a C3-C4 benzene ring structure doped with 1-3 N atoms. 25 A nitrogen-containing aromatic group; R 10 -R 13 Each independently selected from any one of the following structures: hydrogen, nitro, cyano, C1-C 15 Alkyl, C1-C 15 Alkoxy, C1-C 15 Alkylthio, -C(=O)-R 16 , halogen-substituted C1-C 15 Alkyl, C1-C 15 Alkoxy or C1-C 15 an alkylthio group; M is selected from a single bond or -C(=O)-; R 14 Select any one of the following structures: C1-C 15 Alkyl, C1-C 15 Alkoxy, C3-C 15 Cycloalkyl, C6-C 15 Aryl, C3-C 15 Heterocycloalkyl, C4-C 15 Heteroaryl, C1-C 15 Alkyl or C1-C 15 Alkoxy, substituted C3-C 15 Cycloalkyl, C6-C 15 Aryl, C3-C 15 Heterocycloalkyl or C4-C 15 heteroaryl; R 15 Select any one of the following structures: C1-C 15 Alkyl, C1-C 15 Alkoxy, C3-C 15 Cycloalkyl, C3-C 15 Heterocycloalkyl, C4-C 15 Heteroaryl, C6-C 15 Aryl, halogen-substituted C1-C 15 Alkyl or C1-C 15 Alkoxy, substituted C3-C 15 Cycloalkyl, C6-C 15 Aryl, C3-C 15 Heterocycloalkyl or C4-C 15 heteroaryl; R 16 Select any one of the following structures: C3-C 15 Cycloalkyl, C3-C 15 Heterocycloalkyl, C4-C15 heteroaryl, C6-C 15 Aryl, substituted C3-C 15 Cycloalkyl, C6-C 15 Aryl, C3-C 15 Heterocycloalkyl or C4-C 15 The heteroaryl group.

2. A carbazole photoinitiator according to claim 1, characterized in that: The R9 is a structure shown in formula (2): In formula (2), X is CH and / or N, and the number of X being N is 1 to 3 non-adjacent ones; 1-2 hydrogen atoms in formula (2) are substituted by nitro, cyano, amine, C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 haloalkyl, C3-C 15 Cycloalkyl, C3-C 15 Heterocycloalkyl, C6-C 12 Aryl, C4-C 15 heteroaryl, and / or substituted C3-C 15 Cycloalkyl, C6-C 15 Aryl, C3-C 15 Heterocycloalkyl or C4-C 15 The heteroaryl group is substituted.

3. A carbazole photoinitiator according to claim 1 or 2, characterized in that: The C3-C 15 The heterocycloalkyl group is a five-membered ring, a six-membered ring, or a benzo-five-membered ring containing 1-2 of N, O, or S; The C6-C 12 The aryl group is phenyl, tolyl, mesityl, biphenyl or naphthyl; The C3-C 15 The cycloalkyl group is a structure shown in formula (3): In formula (3), the value range of n is 0-5; the value range of m is 1-5; The C4-C 15 The heteroaryl group is a structure shown in formula (4): In formula (4), Y is O, S, S(=O) or S(=O)2; p is in the range of 0-5; R 17 -R 19 are independently selected from any one of the following structures: hydrogen, C1-C5 alkyl, C1-C5 alkoxy; or, R 17 and R 18， or R 18 and R 19 Any pair in -C(R 20 )=C(R 21 )-C(R 22 )=C(R 23 )-; where R 20 -R 23 Each of them is independently selected from any one of the following structures: hydrogen, C1-C5 alkyl, C1-C5 alkoxy.

4. A carbazole photoinitiator according to claim 1 or 2, characterized in that: Substituted C3-C 15 Cycloalkyl, C6-C 15 Aryl, C3-C 15 Heterocycloalkyl or C4-C 15 The heteroaryl group is specifically cyano, nitro, C1-C8 alkyl, C1-C8 alkoxy, C1-C8 haloalkyl, C1-C8 haloalkoxy, C3-C 15 Cycloalkyl, C3-C 15 C3-C8 substituted with at least one of heterocycloalkyl, C1-C8 cycloalkoxy, and C1-C8 heterocycloalkoxy 15 Cycloalkyl, C6-C 15 Aryl, C3-C 15 Heterocycloalkyl or C4-C 15 The heteroaryl group, wherein the C1-C8 alkyl group, the C1-C8 alkoxy group, the C1-C8 haloalkyl group and the C1-C8 haloalkoxy group are not interrupted or are interrupted by at least one O.

5. The carbazole photoinitiator according to claim 1, characterized in that: The R 16 It is an unsaturated five-membered ring group containing 1-2 heteroatoms among N, O, and S, an unsaturated six-membered ring, or a condensed ring group formed by the fusion of an unsaturated six-membered ring and an unsaturated five-membered ring group, or an unsaturated five-membered ring group containing 1-2 heteroatoms among N, O, and S, an unsaturated six-membered ring, or a condensed ring group formed by the fusion of an unsaturated six-membered ring and an unsaturated five-membered ring group substituted with at least one group selected from C1-C5 alkyl or C1-C5 alkoxy.

6. The carbazole photoinitiator according to claim 1, characterized in that: The structure of the carbazole photoinitiator is any one of the following:

7. A photopolymerizable composition, characterized in that The invention comprises the following components (a) to (b): (a) at least one ethylenically unsaturated photopolymerizable compound; (b) a photoinitiator, wherein the photoinitiator comprises the carbazole photoinitiator as claimed in any one of claims 1 to 6.

8. A photopolymerizable composition according to claim 7, characterized in that The ethylenically unsaturated photopolymerizable compound is a resin obtained by reacting a saturated or unsaturated polyacid anhydride, an epoxy resin, and an unsaturated monocarboxylic acid.

9. A photopolymerizable composition according to claim 7, characterized in that: The photoinitiator further comprises at least one second photoinitiator and / or additive.

10. An application of a carbazole photoinitiator, characterized in that: The carbazole photoinitiator according to any one of claims 1 to 6 is used in photocurable coatings, inks, 3D printing materials or UV-LED curing systems.

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