A triarylboron organic compound and its preparation method and application as an organic photoinitiator

Abstract

The present invention belongs to the technical field of organic compounds, and specifically relates to a class of triaryl boron organic compounds, a preparation method thereof, and an application as an organic photoinitiator. The present invention provides a class of triaryl boron organic compounds, the structure of which is shown in general formula I, with methyl-substituted triphenylborane as an electron acceptor unit, and diphenylamine, carbazole, acridine and other groups and their derivatives as electron donor units. The triaryl boron compound provided by the present invention has excellent light and heat stability, and can be stored and transported under daily conditions; its absorption wavelength can be extended to the visible light region, and has a good molar extinction coefficient in the visible light region. The triaryl boron compound provided by the present invention can be used as a single-component photoinitiator and added to an ordinary photocuring system. The system after addition can effectively initiate photocuring under a light source in the visible light region, and form a pure organic photocurable coating that can emit light under visible light, which has a wide range of uses, including but not limited to photoresist, three-dimensional printing, anti-counterfeiting and other fields.

Description

Technical Field

[0001] The invention belongs to the technical field of organic compounds, and in particular relates to a triarylboron organic compound and a preparation method thereof and an application thereof as an organic photoinitiator. Background Art

[0002] Photocuring technology has the characteristics of high efficiency, environmental protection, energy saving and economy. It has been widely used in photoresist, functional coatings, microelectronic circuits, dental materials and 3D printing.

[0003] Photocuring refers to the process of polymerization and crosslinking of monomers or oligomers under ultraviolet / visible light to achieve curing. Photocuring systems usually include various functionalized polymer monomers, oligomers, photoinitiators, etc. After ultraviolet / visible light irradiation, the ground state photoinitiator molecules absorb photons and enter the excited state to produce active initiating species, inducing the monomers or oligomers in the system to undergo polymerization and crosslinking reactions to form dense polymers. Therefore, despite the small amount used, the photoinitiator is a key component in the photocuring system. Based on the analogy of active intermediates, photoinitiators can be divided into free radical type and cationic type. Free radical photoinitiators are the most widely used. According to their principles, they can be divided into two types: cleavage type and hydrogen abstraction type. The cleavage type photoinitiator undergoes α-cleavage / β-cleavage of its own skeleton under light to produce active initiating species, but its induced polymerization requires high energy, and generally requires a mercury lamp / ultraviolet LED as a light source, which has high energy consumption and produces harmful gas ozone when illuminated. The hydrogen abstraction type photoinitiator itself The skeleton is not destroyed, and it forms an initiation system with the additionally added second component, and produces active initiating species under visible light irradiation. However, the curing process requires two components, photoinitiator and co-initiator, to produce active initiating species, which will be affected by the molecular diffusion rate, resulting in the polymerization rate and monomer conversion rate being significantly lower than those of the cleavage-type photoinitiator. At the same time, the addition of the second component will have an adverse effect on the cured coating, limiting its scope of application.

[0004] With the application of photocuring technology in some cutting-edge technologies, the requirements for photoinitiators and cured graphics are getting higher and higher. However, the commonly used cleavage-type photoinitiators, such as oxime ester compounds, have low stability, which is not conducive to storage and transportation at room temperature. There are also problems such as yellowing of the cured coating and bubbles generated during curing, which lead to decreased transparency and density of the coating. Although the two-component hydrogen-abstracting photoinitiator can overcome the above shortcomings, it has obvious defects such as slow polymerization rate and low monomer conversion rate. In addition, the commonly used second components such as tertiary amines and iodonium salts have problems such as strong odor on the cured coating.

[0005] Therefore, researching and developing pure organic single-component photoinitiators with good stability and convenient storage and transportation at room temperature is of great significance to the expanded application of photocuring technology. Summary of the invention

[0006] The purpose of the present invention is to provide a class of triaryl boron organic compounds and a preparation method thereof and an application as an organic photoinitiator. The triaryl boron organic compound provided by the present invention has high light / thermal stability and a good molar extinction coefficient in the visible light region. It can be used as a single-component photoinitiator and can effectively initiate photocuring under a light source of LED (light-emitting diode) 405nm visible light region, and is applied to the fields of photoresist, three-dimensional printing, etc.

[0007] In order to achieve the above object, the present invention provides the following technical solutions:

[0008] The present invention provides a triarylboron organic compound having the general structural formula shown in Formula I:

[0009]

[0010] The structure of the D group in the general formula I is shown in formula a, formula b, formula c, formula d or formula e:

[0011]

[0012] In formula a, formula b, formula c, formula d, and formula e, R is a hydrogen atom, an alkoxy group, a halogen, a hydroxyl group, a nitro group, a cyano group, an alkanoyloxy group, an unsubstituted or substituted C 1-20 Straight or branched alkyl, C 3-20 cycloalkyl, alkyl-substituted cycloalkyl, phenyl, C 4-20 alkyl substituted phenyl or biphenyl; the substituted C 1-20 The substituent of the straight chain or branched alkyl group is one or more of a cycloalkyl group, an amide group, a hydroxyl group, an alkoxy group and an alkylthio group; the cycloalkyl-substituted C 1-20 The total number of carbon atoms in a straight or branched alkyl group is C 4-20 The total number of carbon atoms in the alkyl-substituted cycloalkyl group is C 4-20 .

[0013] Preferably, in formula a, R is a hydrogen atom, a halogen, a hydroxyl group, an alkoxy group, an unsubstituted or substituted C 1-20 A straight or branched alkyl group, a phenyl group or a biphenyl group;

[0014] In formula b, R is a hydrogen atom, a halogen, an alkoxy group, or an unsubstituted or substituted C 1-20 A straight chain or branched alkyl group;

[0015] In formula c, R is a hydrogen atom, a halogen, a hydroxyl group, an alkoxy group, an unsubstituted or substituted C 1-20 A straight or branched alkyl or phenyl group;

[0016] In formula d, R is a hydrogen atom, a halogen, a hydroxyl group, an alkoxy group, or an unsubstituted or substituted C 1-20 A straight chain or branched alkyl group;

[0017] In formula e, R is a hydrogen atom, a halogen, a hydroxyl group, an alkoxy group, an unsubstituted or substituted C 1-20 A straight chain or branched chain alkyl or phenyl group.

[0018] Preferably, the D group has any one of the following structures:

[0019]

[0020] Preferably, it has any one of the following structures:

[0021]

[0022]

[0023] The present invention provides a method for preparing the triarylboron organic compound described in the above technical solution, comprising the following steps:

[0024] The compound of formula 2, DH compound, organic palladium catalyst and acid binding agent are subjected to Buchwald-Hartwig coupling reaction in an organic solvent to obtain a triarylboron organic compound of formula I;

[0025]

[0026] Preferably, the method for preparing the compound of the structure shown in Formula 2 comprises the following steps:

[0027] Di(trimethylphenyl)boron fluoride, 2,5-dibromo-m-xylene and n-butyl lithium are subjected to a nucleophilic substitution reaction in a solvent to obtain a compound shown in formula 2.

[0028] The present invention provides the use of the triaryl boron organic compound described in the above technical solution or the triaryl boron organic compound prepared by the preparation method described in the above technical solution as an organic photoinitiator.

[0029] The present invention provides a photocurable material, wherein the raw materials of the photocurable material include a prepolymerized photosensitive resin, an active monomer and a photoinitiator; the photoinitiator is the triaryl boron organic compound described in the above technical scheme or the triaryl boron organic compound prepared by the preparation method described in the above technical scheme as an organic photoinitiator.

[0030] Preferably, the prepolymerized photosensitive resin is a resin having a vinyl group; and the active monomer is a monomer having a vinyl group.

[0031] Preferably, the raw materials of the photocurable material further include one or more of a colorant, a solvent, a photocrosslinking agent, a photosensitizer, an antioxidant, a surfactant, a curing accelerator and a thermal polymerization inhibitor.

[0032] The present invention provides a type of triaryl boron organic compound having the general structural formula shown in Formula I. The triaryl boron organic compound provided by the present invention has methyl-substituted triphenylborane as the electron acceptor (A) unit; and diphenylamine, carbazole, acridine and other groups and their derivatives as the electron donor (D) unit. The triaryl boron organic compound provided by the present invention has the following beneficial effects: (1) The triaryl boron organic compound provided by the present invention has good light stability and thermal stability, and has good room temperature storage and transportation performance. (2) The triaryl boron-containing compound provided by the present invention has a high generation rate of long-lived excited triplet species under light excitation, and can initiate monomer polymerization under a single component, without the need to add a second component to form an initiation system, thereby eliminating the damage of the second component to the properties of the photocurable coating, such as the yellowing problem. (3) The absorption wavelength of the triarylboron compound provided by the present invention is red-shifted to the visible light region, and has a good molar extinction coefficient in the visible light region. It can effectively initiate photocuring under the light source of LED (light-emitting diode) 405nm visible light region. The curing efficiency at this wavelength is significantly higher than that of commercial oxime ester photoinitiators that mainly work under ultraviolet light sources. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is the test data of the solvation effect of the absorption spectrum of the photoinitiator A1;

[0034] Figure 2 Light stability test data for photoinitiators A1, A4, A7, A8, A10, A12, A13, A14, A17, A20, A22, A23, A25, A27, A30;

[0035] Figure 3 The pattern of photoinitiator A1 was cured under 405 nm visible light irradiation. DETAILED DESCRIPTION

[0036] The present invention provides a triarylboron organic compound having the general structural formula shown in Formula I:

[0037]

[0038] The structure of the D group in the general formula I is shown in formula a, formula b, formula c, formula d, formula e, formula f, or formula g:

[0039]

[0040] In formula a, formula b, formula c, formula d, and formula e, R is a hydrogen atom, an alkoxy group, a halogen, a hydroxyl group, a nitro group, a cyano group, an alkanoyloxy group, an unsubstituted or substituted C 1-20 Straight or branched alkyl, C 3-20 cycloalkyl, alkyl-substituted cycloalkyl, phenyl, C 4-20 alkyl substituted phenyl or biphenyl; the substituted C1-20 The substituent of the straight chain or branched alkyl group is one or more of a cycloalkyl group, an amide group, a hydroxyl group, an alkoxy group or an alkylthio group; the cycloalkyl-substituted C 1-20 The total number of carbon atoms in a straight or branched alkyl group is C 4-20 The total number of carbon atoms in the alkyl-substituted cycloalkyl group is C 4-20 ;

[0041] In the present invention, R in formula a is preferably a hydrogen atom, a halogen, a hydroxyl group, an alkoxy group, an unsubstituted or substituted C 1-20 The halogen is preferably F, Cl or Br. The alkoxy is preferably C 1-3 Alkoxy, specifically preferably methoxy. The unsubstituted C 1-20 The straight or branched alkyl group is preferably an unsubstituted C 1-10 A straight chain or branched alkyl group, more preferably an unsubstituted C 1-5 A straight chain or branched alkyl group, preferably an unsubstituted C 1-4 The straight-chain or branched-chain alkyl group is preferably methyl, isopropyl or tert-butyl.

[0042] In the present invention, R in formula b is a hydrogen atom, a halogen, an alkoxy group or an unsubstituted or substituted C 1-20 The halogen is preferably F, Cl or Br. The alkoxy is preferably C 1-3 Alkoxy, specifically preferably methoxy. The unsubstituted C 1-20 The straight or branched alkyl group is preferably an unsubstituted C 1-10 A straight chain or branched alkyl group, more preferably an unsubstituted C 1-5 A straight chain or branched alkyl group, preferably an unsubstituted C 1-4 The straight chain or branched chain alkyl group is preferably a methyl group or a tert-butyl group.

[0043] In the present invention, R in formula c is preferably a hydrogen atom, a halogen, a hydroxyl group, an alkoxy group, an unsubstituted or substituted C 1-20 The halogen is preferably F, Cl or Br. The alkoxy is preferably C 1-3 Alkoxy, specifically preferably methoxy. The unsubstituted C 1-20 The straight or branched alkyl group is preferably an unsubstituted C 1-10 A straight chain or branched alkyl group, more preferably an unsubstituted C 1-5 A straight chain or branched alkyl group, preferably an unsubstituted C 1-4 The straight-chain or branched-chain alkyl group is preferably methyl, isopropyl or tert-butyl.

[0044] In the present invention, R in formula d is a hydrogen atom, a halogen, a hydroxyl group, an alkoxy group, or an unsubstituted or substituted C 1-20 The halogen is preferably F, Cl or Br. The alkoxy is preferably C 1-3 Alkoxy, specifically preferably methoxy. The unsubstituted C 1-20 The straight or branched alkyl group is preferably an unsubstituted C 1-10 A straight chain or branched alkyl group, more preferably an unsubstituted C 1-5 A straight chain or branched alkyl group, preferably an unsubstituted C 1-4 The straight chain or branched chain alkyl group is preferably a methyl group or a tert-butyl group.

[0045] In the present invention, R in formula e is preferably a hydrogen atom, a halogen, a hydroxyl group, an alkoxy group, an unsubstituted or substituted C 1-20 The halogen is preferably F, Cl or Br. The alkoxy is preferably C 1-3 Alkoxy, specifically preferably methoxy. The unsubstituted C 1-20 The straight or branched alkyl group is preferably an unsubstituted C 1-10 A straight chain or branched alkyl group, more preferably an unsubstituted C 1-5 A straight chain or branched alkyl group, preferably an unsubstituted C 1-4 The straight chain or branched chain alkyl group is preferably a methyl group or a tert-butyl group.

[0046] In the present invention, the D group preferably has any one of the following structures:

[0047]

[0048] In a specific embodiment of the present invention, the triarylboron organic compound of the general structural formula shown in Formula I preferably has any one of the following structures:

[0049]

[0050]

[0051] The present invention provides a method for preparing the triarylboron organic compound described in the above technical solution, comprising the following steps:

[0052] A compound of formula 2, a DH compound, an organic palladium catalyst and an acid-binding agent are subjected to a Buchwald-Hartwig coupling reaction in an organic solvent (hereinafter referred to as the first organic solvent) to obtain a triarylboron organic compound of formula I;

[0053]

[0054] In the present invention, unless otherwise specified, all preparation raw materials / components are commercially available products well known to those skilled in the art.

[0055] In the present invention, the preparation method of the compound of the structure shown in Formula 2 preferably includes the following steps: di(trimethylphenyl)boron fluoride, 2,5-dibromo-m-xylene and n-butyl lithium are subjected to a nucleophilic substitution reaction in an organic solvent (hereinafter referred to as the second organic solvent) to obtain the compound shown in Formula 2. In the present invention, the second organic solvent is preferably N,N-dimethylformamide. The molar ratio of the di(trimethylphenyl)boron fluoride and the 2,5-dibromo-m-xylene is preferably 3.73:5.59. The molar ratio of the di(trimethylphenyl)boron fluoride and n-butyl lithium is preferably 3.73:4.10. The present invention has no special requirements for the amount of the second organic solvent, as long as the nucleophilic substitution reaction is carried out smoothly. In the present invention, the nucleophilic substitution reaction is carried out in a protective gas atmosphere, and the protective gas is preferably argon or nitrogen. The nucleophilic substitution reaction preferably includes the following steps: dissolving 2,5-dibromo-meta-xylene in part of the second organic solvent to obtain a 2,5-dibromo-meta-xylene solution; adding n-butyl lithium to the 2,5-dibromo-meta-xylene solution at 77K to carry out a first-stage nucleophilic substitution reaction to obtain a first-stage nucleophilic substitution reaction liquid; dissolving di(trimethylphenyl) boron fluoride in the remaining second organic solvent to obtain a di(trimethylphenyl) boron fluoride solution; heating the first-stage nucleophilic substitution reaction liquid to room temperature and then adding the di(trimethylphenyl) boron fluoride solution to carry out a second-stage nucleophilic substitution reaction to obtain a nucleophilic substitution reaction liquid. The time for the first-stage nucleophilic substitution reaction is preferably 2h. The time for the second-stage nucleophilic substitution reaction is preferably 24h.

[0056] In the present invention, after the nucleophilic substitution reaction, a nucleophilic substitution reaction liquid is obtained. In the present invention, the nucleophilic substitution reaction liquid is preferably post-treated to obtain the compound of the structure shown in Formula 2. In the present invention, the post-treatment preferably includes the following steps: removing the solvent from the nucleophilic substitution reaction liquid to obtain a residue; purifying the residue by column chromatography to obtain a pure compound of the structure shown in Formula 2. In the present invention, the specific implementation of the solvent removal is preferably evaporation; the eluent used for the column chromatography purification is preferably a mixed solvent of petroleum ether (PE) and dichloromethane (DCM), and the volume ratio of PE to DCM is preferably 10 to 50:1.

[0057] In the present invention, the DH has any one of the following structures:

[0058]

[0059]

[0060] In the present invention, the palladium catalyst is preferably diphenylphosphinocene palladium dichloride, tetrakistriphenylphosphine palladium or dichlorobistriphenylphosphine palladium. The acid binding agent is preferably sodium tert-butoxide, cesium carbonate or potassium carbonate. The first organic solvent is preferably one or more of benzene, toluene, xylene, chlorobenzene, dichlorobenzene, tetrahydrofuran, dioxane, nitrogen-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, cyclopentane, acetonitrile and benzonitrile. The molar ratio of the compound of the structure shown in Formula 2 to DH is preferably 4.24-10:5.08-12, more preferably 4.4-8:5.1-10. The molar ratio of the compound of the structure shown in Formula 2 to the palladium catalyst is preferably 4.24-10:0.2-0.5, more preferably 4.4-8:0.3-0.45. The molar ratio of the compound of the structure shown in Formula 2 to the acid binding agent is preferably 4.24-10:12.7-30, and more preferably 4.4-8:13-28. The present invention has no special requirements for the amount of the first organic solvent, as long as the Buchwald-Hartwig coupling reaction is carried out smoothly. In the present invention, the temperature of the Buchwald-Hartwig coupling reaction is preferably 110-160°C, and the insulation time of the Buchwald-Hartwig coupling reaction is preferably 12-24h. In the present invention, the Buchwald-Hartwig coupling reaction is preferably carried out in a protective gas atmosphere, and the protective gas is preferably argon or nitrogen. The Buchwald-Hartwig coupling reaction is preferably carried out under stirring.

[0061] In the present invention, the Buchwald-Hartwig coupling reaction is followed by obtaining a Buchwald-Hartwig coupling reaction liquid. The present invention preferably performs post-treatment on the Buchwald-Hartwig coupling reaction liquid to obtain the compound having the structure shown in Formula 1. In the present invention, the post-treatment preferably comprises the following steps: the Buchwald-Hartwig coupling reaction liquid is cooled to room temperature and mixed with water, and the obtained liquid phase component is extracted with dichloromethane (DCM) to obtain an extracted organic phase; the extracted organic phase is dried and solvent removed to obtain a crude compound having the structure shown in Formula 1; the crude compound having the structure shown in Formula 1 is purified by column chromatography to obtain a pure compound having the structure shown in Formula 1. In the present invention, the number of extractions is preferably 3 times, and the reagent used for drying is preferably anhydrous sodium sulfate. The specific implementation of the solvent removal is preferably reduced pressure rotary evaporation; the eluent used for column chromatography purification is preferably a mixed solvent of petroleum ether (PE) and dichloromethane (DCM), and the volume ratio of PE to DCM is preferably 10 to 50:1.

[0062] The present invention provides the use of the triarylboron organic compound described in the above technical solution or the triarylboron organic compound prepared by the preparation method described in the above technical solution as an organic photoinitiator. In the present invention, the organic photoinitiator is an initiator having visible light initiation performance or visible light induced polymerization performance.

[0063] The present invention provides a photocurable material, wherein the raw materials of the photocurable material include a prepolymerized photosensitive resin, an active monomer and a photoinitiator; the photoinitiator is the triaryl boron organic compound described in the above technical solution or the triaryl boron organic compound prepared by the preparation method described in the above technical solution.

[0064] In the present invention, the prepolymerized photosensitive resin is preferably a resin having a vinyl group. The reactive monomer is preferably a monomer having a vinyl group. In the present invention, the raw material of the photocurable material is preferably photocurable under visible light conditions.

[0065] In the present invention, the raw materials of the photocurable material preferably further include one or more of a colorant, a solvent, a photocrosslinking agent, a photosensitizer, an antioxidant, a surfactant, a curing accelerator and a thermal polymerization inhibitor.

[0066] As one or more embodiments of the present invention, the photocurable material is specifically a photocurable coating.

[0067] In the present invention, in the photocurable material, the mass percentage of the triarylboron organic compound having the structure represented by Formula 1 is preferably 0.0001 to 10%, more preferably 0.001 to 8%, and further preferably 0.01 to 5%.

[0068] In the present invention, the photocurable material preferably includes the following raw materials in parts by weight:

[0069] 100 parts of prepolymerized photosensitive resin, 70 parts of active monomers, and 0.017-15 parts of photoinitiator; the raw materials of the photocurable material preferably also include a solvent, and the solvent is preferably acetone.

[0070] In the present invention, in the photocurable material, the mass percentage of the photoinitiator is preferably 0.05-8%, specifically preferably 0.05%, 3%, 2%, 5%, 2%, 7%, 4%, 0.06%, 6%, 0.08% or 8%.

[0071] In the present invention, the prepolymerized photosensitive resin is preferably a methacrylate / methacrylic acid / methyl methacrylate copolymer, the molar ratio of methacrylate, methacrylic acid and methyl methacrylate is 50:15:30, and the Mw of the prepolymerized photosensitive resin is preferably 70000. In the present invention, the active monomer is preferably tripropylene glycol diacrylate (TPGDA).

[0072] In the present invention, the preparation method of the photocurable material preferably includes the following steps: dissolving the prepolymerized photosensitive resin, the active monomer and the photoinitiator in an organic solvent to obtain a mixture; applying the mixture to the surface of the PET template to obtain a wet film; heating the wet film to remove the solvent to obtain a dry film; exposing the dry film to light-curing to obtain a photocurable material. In the present invention, the thickness of the wet film is preferably 2 μm, and the temperature of the solvent removal is preferably 90°C; during the light curing, the present invention preferably attaches a mask to the dry film. The light source for the exposure is preferably a 405nm LED surface light source.

[0073] In order to further illustrate the present invention, the technical solution provided by the present invention is described in detail below in conjunction with the accompanying drawings and embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0074] Example 1

[0075] The synthesis route of the three aryl compounds A1 in this embodiment is:

[0076]

[0077] (1) Synthesis of intermediate 1

[0078] In a nitrogen atmosphere, 2,5-dibromo-m-xylene (1.48 g, 5.59 mmol) and N,N-dimethylformamide (30 mL) were added to a 100 mL reaction bottle. At 77 K, n-butyllithium (2.56 mL, 4.10 mmol) was added dropwise to the reaction bottle. After reacting at low temperature for 2 hours, the temperature was slowly raised to room temperature. A solution of di(trimethylphenyl)boron fluoride (1 g, 3.73 mmol) in N,N-dimethylformamide was added dropwise to the reaction bottle. The reaction was carried out at room temperature for 24 hours. After the reaction was completed, the solvent was evaporated to dryness, and PE:DCM=50:1 was used as the eluent. The obtained residue was separated by column chromatography, and the corresponding components were collected to obtain pure intermediate 1. HRMS found: 432.1624.1HNMR(400MHz, CDCl3)δ7.48(d,2H),6.81(s,4H),2.43(s,12H),2.13(s,6H).

[0079] (2) Synthesis of photoinitiator A1

[0080] In a nitrogen atmosphere, intermediate 1 (1 g, 2.31 mmol), diphenylamine (1.95 g, 11.54 mmol), tetrakis(triphenylphosphine)palladium (133.37 mg, 0.115 mmol), sodium tert-butoxide (0.665 g, 6.92 mmol) and N,N-dimethylformamide (20 mL) were added to a 100 mL pressure-resistant branch tube and stirred for 12 h under argon at 110 °C. After the reaction returned to room temperature, the reaction solution was poured into water, and the organic phase was collected by extraction with DCM (100 mL × 3) and dried over anhydrous Na2SO4. The organic solvent was removed under reduced pressure, and PE:DCM = 20:1 was used as the eluent. The crude product was purified by flash column chromatography to obtain compound A1. HRMS found: 521.3254. 1 HNMR (400MHz, CDCl3) δ7.29(s,2H),7.26-7.17(m,4H),7.01-6.95(m,4H),6.93(d,2H),6.84(s,4H),2.33(s,6H),2.07(s,12H),1.97(s,6H).

[0081] Example 2

[0082] The synthetic route of the three aryl compounds A2 in this embodiment is:

[0083]

[0084] The synthesis method is as in Example 1. replace Synthesized compound A2. HRMS found: 549.3567. 1 H NMR (400MHz, CDCl3) δ7.26-7.17(m,4H),7.01-6.95(m,4H),6.93(s,2H),6.84(s,4H),2.33(s,6H),2.31(s,6H),2.07(s,12H),1.97(s,6H).

[0085] Example 3

[0086] The synthetic route of the triarylboron compound A3 in this embodiment is:

[0087]

[0088] The synthesis method is as in Example 1. replace Synthesized compound A3. HRMS found: 605.4193. 1H NMR(400MHz, CDCl3)δ7.29(s,2H),7.26-7.17(m,4H),7.01-6.95(m,4H),6.93(d,2H) ),6.84(s,4H),2.87(m,4H),2.33(s,6H),2.07(s,12H),1.97(s,6H),1.22(dd,12H).

[0089] Example 4

[0090] The synthetic route of the triarylboron compound A4 in this example is:

[0091]

[0092] The synthesis method is as in Example 1. replace Synthesized compound A4. HRMS found: 553.3152. 1 H NMR (400MHz, CDCl3) δ7.08-6.98(m,10H),6.81(dt,4H),2.33(s,6H),2.07(s,12H),1.97(s,6H).

[0093] Example 5

[0094] The synthetic route of triarylboron compound A5 in this example is:

[0095]

[0096] The synthesis method is as in Example 1. replace Synthesis of compound A5. HRMS found: 581.3465. 1 H NMR (400MHz, CDCl3) δ7.18(td,4H),7.07(s,2H),6.84(s,4H),6.74(dt,4H),3.81(s,6H),2.33(s,6H),2.07(s,12H),1.97(s,6H).

[0097] Example 6

[0098] The synthetic route of triarylboron compound A6 in this example is:

[0099]

[0100] The synthesis method is as in Example 1. replace Synthesized compound A6. HRMS found: 677.1464. 1H NMR (400MHz, CDCl3) δ7.38(td,4H),7.26-7.17(m,6H),6.93(d,2H),6.84(s,4H),2.33(s,6H),2.07(s,12H),1.97(s,6H).

[0101] Example 7

[0102] The synthetic route of the triarylboron compound A7 in this example is:

[0103]

[0104] The synthesis method is as in Example 1. replace Synthesis of compound A7. HRMS found: 673.3880. 1 H NMR (400MHz, CDCl3) δ7.75(dd,4H),7.55-7.41(m,14H),6.93(s,2H),6.84(s,4H),2.33(s,6H),2.07(s,12H),1.97(s,6H).

[0105] Example 8

[0106] The synthetic route of triarylboron compound A8 in this example is:

[0107]

[0108] (1) The synthesis of intermediate 1 is the same as that of Example 1.

[0109] (2) Synthesis of photoinitiator A8

[0110] In a nitrogen atmosphere, intermediate 1 (1 g, 2.31 mmol), diphenylsilane (4.03 g, 11.54 mmol), tetrakis(triphenylphosphine)palladium (133.37 mg, 0.115 mmol), sodium tert-butoxide (0.665 g, 6.92 mmol) and dimethyl sulfoxide (20 mL) were added to a 100 mL pressure-resistant branch tube and stirred for 12 h under argon at 110 °C. After the reaction returned to room temperature, the reaction solution was poured into water, and the organic phase was collected by extraction with DCM (100 mL × 3) and dried over anhydrous Na2SO4. The organic solvent was removed under reduced pressure, and PE:DCM = 30:1 was used as the eluent. The crude product was purified by flash column chromatography to obtain compound A8. HRMS found: 701.3649. 1H NMR (400MHz, CDCl3) δ7.64-7.25(m,18H),7.00-6.98(t,2H),6.87(s,4H),2.33(s,6H),2.07(s,12H),1.97(s,6H).

[0111] Example 9

[0112] The synthetic route of triarylboron compound A9 in this example is:

[0113]

[0114] The synthesis method is as shown in Example 8. replace Synthesis of compound A9. HRMS found: 729.3962. 1 H NMR(400MHz, CDCl3)δ7.45-7.38(m,8H),7.26-7.19(m,6H),7.07(s,2H),7.0 1(td,2H),6.87(s,4H),2.41(s,6H),2.33(s,6H),2.07(s,12H),1.97(s,6H).

[0115] Example 10

[0116] The synthetic route of the triarylboron compound A10 in this example is:

[0117]

[0118] The synthesis method is as shown in Example 8. replace Synthesis of compound A10. HRMS found:813.4901. 1 H NMR(400MHz, CDCl3)δ7.45-7.38(m,8H),7.26-7.19(m,6H),7.07(s,2H),7.01(td,2 H),6.87(s,4H),2.41(s,6H),2.33(s,6H),2.07(s,12H),1.97(s,6H),1.31(s,18H).

[0119] Embodiment 11

[0120] The synthetic route of the triarylboron compound A11 in this example is:

[0121]

[0122] The synthesis method is as shown in Example 8. replace Synthesized compound A11. HRMS found: 761.3860. 1 H NMR (400MHz, CDCl3) δ7.41(m,12H),7.28(dd,2H),7.03(m,8H),3.81(s,6H),2.33(s,12H),2.18(s,6H),2.02(s,6H).

[0123] Example 12

[0124] The synthetic route of the triarylboron compound A12 in this example is:

[0125]

[0126] The synthesis method is as shown in Example 8. replace Synthesis of compound A12. HRMS found: 857.1859. 1 H NMR (400MHz, CDCl3) δ7.64(dt,4H),7.42-7.28(m,10H),7.07-7.01(m,4H),6.87(s,4H),2.41(s,6H),2.33(s,6H),2.07(s,12H),1.97(s,6H).

[0127] Example 13

[0128] The synthetic route of the triarylboron compound A13 in this example is:

[0129]

[0130] (1) The synthesis of intermediate 1 is the same as that of Example 1.

[0131] (2) Synthesis of photoinitiator A13

[0132] In a nitrogen atmosphere, intermediate 1 (1 g, 2.31 mmol), dimethylacridine (2.42 g, 11.54 mmol), dichlorobistriphenylphosphine palladium (102.53 mg, 0.115 mmol), sodium tert-butoxide (0.665 g, 6.92 mmol) and dimethyl sulfoxide (20 mL) were added to a 100 mL pressure-resistant branch tube and stirred for 16 h under argon at 110 ° C. After the reaction returned to room temperature, the reaction solution was poured into water, and the organic phase was collected by extraction with DCM (100 mL × 3) and dried over anhydrous Na2SO4. The organic solvent was removed under reduced pressure, and PE:DCM = 30:1 was used as the eluent. The crude product was purified by flash column chromatography to obtain compound A13. HRMS found: 561.3567. 1H NMR (400MHz, CDCl3) δ7.23-7.14(m,6H),7.07(s,2H),7.01-6.95(m,6H),2.32(s,12H),2.18(s,6H)2.09(s,6H),1.67(s,6H).

[0133] Embodiment 14

[0134] The synthetic route of the triarylboron compound A14 in this example is:

[0135]

[0136] The synthesis method is as in Example 13. replace Synthesized compound A14. HRMS found: 589.3880. 1 H NMR (400MHz, CDCl3) δ7.19(dd,2H),7.09-7.01(m,6H),6.87(s,4H),2.34(s,12H),2.31(s,6H),2.18(s,6H),2.09(s,6H),1.67(s,6H).

[0137] Embodiment 15

[0138] The synthetic route of the triarylboron compound A15 in this example is:

[0139]

[0140] The synthesis method is as in Example 13. replace Synthesized compound A15. HRMS found: 645.4506. 1 H NMR(400MHz, CDCl3)δ7.19(dd,2H),7.09-7.01(m,6H),6.87(s,4H),2.87(m,2H), 2.34(s,12H),2.31(s,6H),2.18(s,6H),2.09(s,6H),1.69(s,6H),1.21(dd,12H).

[0141] Example 16

[0142] The synthetic route of the triarylboron compound A16 in this example is:

[0143]

[0144] The synthesis method is as in Example 13. replace Synthesized compound A16. HRMS found: 593.3465.1H NMR (400MHz, CDCl3) δ9.29 (s, 2H), 7.16 (s, 2H), 7.08-6.92 (m, 6H), 6.73-6.65 (m, 4H), 2.32 (s, 12H), 2.18 (s, 6H), 2.09 (s, 6H), 1.67 (s, 6H).

[0145] Embodiment 17

[0146] The synthetic route of the triarylboron compound A17 in this example is:

[0147]

[0148] The synthesis method is as in Example 13. replace Synthesis of compound A17. HRMS found: 621.3778. 1 H NMR(400MHz, CDCl3)δ7.21(d,2H),7.07(s,2H),6.87(s,4H),6.72(s,2H),6.6 9(dd,2H),3.71(s,6H),2.32(s,12H),2.18(s,6H),2.09(s,6H),1.67(s,6H).

[0149] Embodiment 18

[0150] The synthetic route of the triarylboron compound A18 in this example is:

[0151]

[0152] The synthesis method is as in Example 13. replace Synthesized compound A18. HRMS found: 717.1777. 1 H NMR (400MHz, CDCl3) δ7.30-7.28(m,4H),7.06(m,4H),6.89(s,4H),2.32(s,12H),2.18(s,6H),2.11(s,6H),1.67(s,6H).

[0153] Embodiment 19

[0154] The synthetic route of the triarylboron compound A19 in this example is:

[0155]

[0156] The synthesis method is as in Example 13. replace Synthesis of compound A19. HRMS found:713.4193. 1 H NMR (400MHz, CDCl3) δ7.75-7.69(m,6H),7.49-7.36(m,10H),7.07(s,2H),7. 05(s,2H),6.87(s,4H),2.32(s,12H),2.18(s,6H),2.09(s,6H),1.67(s,6H).

[0157] Embodiment 20

[0158] The synthetic route of the triarylboron compound A20 in this example is:

[0159]

[0160] (1) The synthesis of intermediate 1 is the same as that of Example 1.

[0161] (2) Synthesis of photoinitiator A20

[0162] In a nitrogen atmosphere, intermediate 1 (1 g, 2.31 mmol), diphenylacridine (3.85 g, 11.54 mmol), diphenylphosphinothiocene palladium dichloride (132.56 mg, 0.115 mmol), sodium tert-butoxide (0.665 g, 6.92 mmol) and dimethyl sulfoxide (20 mL) were added to a 100 mL pressure-resistant branch tube and stirred at 130 ° C under argon conditions for 24 h. After the reaction returned to room temperature, the reaction solution was poured into water, and the organic phase was collected by extraction with DCM (100 mL × 3) and dried over anhydrous Na2SO4. The organic solvent was removed under reduced pressure, and PE:DCM = 50:1 was used as the eluent. The crude product was purified by flash column chromatography to obtain compound A20. HRMS found: 685.3880. 1 H NMR (400MHz, CDCl3) δ7.23-7.06(m,18H),7.02(s,2H),6.87(s,4H),2.33(s,6H),2.07(s,12H),1.97(s,6H).

[0163] Embodiment 21

[0164] The synthetic route of the triarylboron compound A21 in this example is:

[0165]

[0166] The synthesis method is as in Example 20, using replace Synthesis of compound A21. HRMS found:713.4193.1 H NMR(400MHz, CDCl3)δ7.45-7.38(m,8H),7.26-7.19(m,6H),7.07(s,2H),7.0 1(td,2H),6.87(s,4H),2.41(s,6H),2.33(s,6H),2.07(s,12H),1.97(s,6H).

[0167] Embodiment 22

[0168] The synthetic route of the triarylboron compound A22 in this example is:

[0169]

[0170] The synthesis method is as in Example 20, using replace Synthesized compound A22. HRMS found: 797.5132. 1 H NMR(400MHz, CDCl3)δ7.45-7.38(m,8H),7.26-7.19(m,6H),7.07(s,2H),7.01(td,2 H),6.87(s,4H),2.41(s,6H),2.33(s,6H),2.07(s,12H),1.97(s,6H),1.31(s,18H).

[0171] Embodiment 23

[0172] The synthetic route of the triarylboron compound A23 in this example is:

[0173]

[0174] The synthesis method is as in Example 20, using replace Synthesized compound A23. HRMS found: 745.4091. 1 H NMR (400MHz, CDCl3) δ7.41(m,12H),7.28(dd,2H),7.03(m,8H),3.81(s,6H),2.33(s,12H),2.18(s,6H),2.02(s,6H).

[0175] Embodiment 24

[0176] The synthetic route of the triarylboron compound A24 in this example is:

[0177]

[0178] The synthesis method is as in Example 20, using replace Synthesis of compound A24. HRMS found: 841.2090. 1 H NMR (400MHz, CDCl3) δ7.64(dt,4H),7.42-7.28(m,10H),7.07-7.01(m,4H),6.87(s,4H),2.41(s,6H),2.33(s,6H),2.07(s,12H),1.97(s,6H).

[0179] Embodiment 25

[0180] The synthetic route of the triarylboron compound A25 in this example is:

[0181]

[0182] (1) The synthesis of intermediate 1 is the same as that of Example 1.

[0183] (2) Synthesis of photoinitiator A25

[0184] In a nitrogen atmosphere, intermediate 1 (1 g, 2.31 mmol), carbazole (1.93 g, 11.54 mmol), diphenylphosphinothiocene palladium dichloride (132.56 mg, 0.115 mmol), sodium tert-butoxide (0.665 g, 6.92 mmol) and N,N-dimethylformamide (30 mL) were added to a 100 mL pressure-resistant branch tube and stirred for 12 h under argon at 120 ° C. After the reaction returned to room temperature, the reaction solution was poured into water, and the organic phase was collected by extraction with DCM (100 mL × 3) and dried over anhydrous Na2SO4. The organic solvent was removed under reduced pressure, and PE:DCM = 30:1 was used as the eluent. The crude product was purified by flash column chromatography to obtain compound A25. HRMS found: 519.3097. 1 HNMR (400MHz, CDCl3) δ8.14(d,2H),7.74(d,2H),7.57(dt,2H),7.50(d,2H),7.25(s,2H),6.87(s,4H),2.32(s,6H),2.13(s,12H),1.92(s,6H).

[0185] Embodiment 26

[0186] The synthetic route of the triarylboron compound A26 in this example is:

[0187]

[0188] The synthesis method is as in Example 25, using replace Synthesis of compound A26. HRMS found: 547.3410. 1 H NMR (400MHz, CDCl3) δ8.14(d,2H),7.74(d,2H),7.50(d,2H),7.25(s,2H),6.87(s,4H),2.46(s,6H),2.32(s,6H),2.13(s,12H),1.92(s,6H).

[0189] Embodiment 27

[0190] The synthetic route of the triarylboron compound A27 in this example is:

[0191]

[0192] The synthesis method is as in Example 25, using replace Synthesized compound A27. HRMS found: 631.4349. 1 H NMR (400MHz, CDCl3) δ8.14(d,2H),7.74(d,2H),7.57(dt,2H),7.50(d,2H),7. 25(s,2H),6.87(s,4H),2.32(s,6H),2.13(s,12H),1.92(s,6H),1.23(s,18H).

[0193] Embodiment 28

[0194] The synthetic route of the triarylboron compound A28 in this example is:

[0195]

[0196] The synthesis method is as in Example 25, using replace Synthesized compound A28. HRMS found: 579.3309. 1 H NMR (400MHz, CDCl3) δ7.72(d,2H),7.58(d,2H),7.33(d,2H),7.25(s,2H),6.87(s,4H),3.81(s,6H),2.32(s,6H),2.13(s,12H),1.92(s,6H).

[0197] Embodiment 29

[0198] The synthetic route of the triarylboron compound A29 in this example is:

[0199]

[0200] The synthesis method is as in Example 25, using replace Synthesized compound A29. HRMS found: 675.1308. 1 H NMR (400MHz, CDCl3) δ8.05(d,2H),7.74(d,2H),7.42(d,2H),7.25(s,2H),6.87(s,4H),2.32(s,6H),2.13(s,12H),1.92(s,6H).

[0201] Embodiment 30

[0202] The synthetic route of the triarylboron compound A30 in this example is:

[0203]

[0204] The synthesis method is as in Example 25, using replace Synthesized compound A30. HRMS found: 671.3723. 1 H NMR(400MHz, CDCl3)δ8.14(d,2H),7.81(s,2H),7.74(d,2H),7.57(t,6H),7.43- 7.35(m,6H),7.16(s,2H),6.87(s,4H),2.32(s,6H),2.13(s,12H),1.92(s,6H).

[0205] Test Example 1

[0206] The photophysical properties of the photoinitiators A1, A4, A7, A8, A10, A12, A13, A14, A17, A20, A22, A23, A25, A27, and A30 obtained in Examples 1, 4, 7, 8, 10, 12, 13, 14, 17, 20, 22, 23, 25, 27, and 30 were studied (the solvent used was acetonitrile, and the test concentration was 1×10 -5 mol / L), the data are shown in Table 1.

[0207] Table 1 Results of photophysical properties study of compounds A1, A4, A7, A8, A10, A12, A13, A14, A17, A20, A22, A23, A25, A27, A30

[0208] Photoinitiator Maximum absorption(nm) Maximum emission (nm) <![CDATA[Molar extinction coefficient (M -1 cm -1 )]]> A1 366 443 22000 A4 367 448 22800 A7 380 463 24500 A8 372 454 25200 A10 375 463 22000 A12 392 485 24400 A13 320 486 19800 A14 323 491 19930 A17 346 514 21540 A-20 381 442 28300 A22 382 445 28500 A23 386 457 28100 A25 370 430 21000 A27 375 435 22400 A30 390 453 23400

[0209] As shown in Table 1, the maximum absorption of compounds A1, A4, A7, A8, A10, A12, A13, A14, A17, A20, A22, A23, A25, A27, and A30 is in the near-visible light region, and there is also strong absorption in the visible light region. Taking molecule A8 as an example, when the electron donor is diphenylsilane, its maximum absorption peak is 372nm. The molar extinction coefficient of the material is calculated using the Lambert-Beer law A=εbc, and its maximum molar extinction coefficient is 25200M -1 cm -1 , 405nm molar extinction coefficient is 16200M -1 cm -1 ; This type of molecule easily absorbs light and generates excited triplet states through intersystem crossing, and this species has a long lifetime and can effectively initiate polymerization.

[0210] Although the photoinitiator A-1 does not absorb strongly in the visible light region, when the polarity of the environment increases, it will have a weak absorption band of n-π* transition at 400-450nm (such as Figure 1 As shown in the figure), it can be attributed to the absorption band with charge transfer properties between the electron-donating group diphenylamine and the electron-withdrawing group triphenylborane of the A1 molecule, which can induce efficient triplet species. Experiments have shown that it also has excellent photocuring performance under a 405nm light source.

[0211] Test Example 2

[0212] The light / thermal stability of A1, A4, A7, A8, A10, A12, A13, A14, A17, A20, A22, A23, A25, A27, and A30 was studied. The thermogravimetric analysis data of the compounds are shown in Table 2. The thermal decomposition temperatures of the above 15 photoinitiators are all greater than 300°C, indicating that this type of compound has excellent thermal stability.

[0213] Table 2 Thermogravimetric analysis results of compounds A1, A4, A7, A8, A10, A12, A13, A14, A17, A20, A22, A23, A25, A27, A30 (Tg onset decomposition temperature / °C)

[0214] A1 A4 A7 A8 A10 A12 A13 A14 A17 A20 A22 A23 A25 A27 A30 Tg 306 308 315 321 329 331 319 318 321 319 325 311 314 312 319

[0215] A1, A4, A7, A8, A10, A12, A13, A14, A17, A20, A22, A23, A25, A27, A30 were prepared as dilute solutions (the solvent was acetonitrile, the test concentration was 1×10 -5 mol / L), and irradiated with 365nm light source for 1 hour, the fluorescence intensity is small (such as Figure 2 The results show that the solutions thereof have high photostability under ultraviolet light, and correspondingly, the solids thereof have better photostability.

[0216] The above tests show that this type of compound has good light stability and thermal stability, allowing it to be stored and transported under daily conditions.

[0217] Test Example 3

[0218] The photopolymerization efficiency of compounds A1, A4, A7, A8, A10, A12, A13, A14, A17, A20, A22, A23, A25, A27, and A30 obtained in Examples 1, 4, 7, 8, 10, 12, 13, 14, 17, 20, 22, 23, 25, 27, and 30 was studied.

[0219] In the polymerization monomer tripropylene glycol diacrylate solution, at least one of the compounds described in the present invention is added as the photoinitiator, and its mass fraction is 0.01-5%, and the oxygen is removed by freezing. The above-mentioned photopolymerization solution is used to prepare a potassium bromide tablet coating with a thickness of about 20 mm. The light source uses a 365nm and 405nm point light source, and the irradiation time is 300s. The polymerization monomer conversion rate is obtained by real-time detection of the change in the characteristic peak area of ​​the carbon-carbon double bond of the polymerization monomer by a Fourier transform infrared spectrometer. The data are shown in Table 3. Except for A13, A14, and A17, three triaryl boron compounds with dimethyl acridine as the electron-donating group, the remaining triaryl boron compounds use 405nm visible light excitation polymerization effect is significantly better than 365nm, indicating that it can be cured with visible light.

[0220] Table 3 Photopolymerization efficiency test results of compounds A1, A4, A7, A8, A10, A12, A13, A14, A17, A20, A22, A23, A25, A27, A30

[0221]

[0222] Application Example 1

[0223] Photocuring component formulation (mass fraction)

[0224] 100 parts of base resin;

[0225] Tripropylene glycol diacrylate (TPGDA) 70 parts;

[0226] Photoinitiator 0.017~15 parts

[0227] Wherein, the base resin is a methacrylate / methacrylic acid / methyl methacrylate copolymer, the molar ratio of methacrylate, methacrylic acid and methyl methacrylate is 50:15:30, the Mw of the base resin is 70000, and 5 mL of acetone is added for dissolution, and the photoinitiator is at least one of the compounds prepared in the above Examples 1 to 45.

[0228] Development exposure

[0229] Take the prepared photocurable component and coat it on the PET template with a wire rod. The film thickness is about 2μm. Dry it at 90℃ for 5min to remove the solvent. Then cool the coated PET plate to room temperature, attach the mask, and expose it with an LED surface light source (405nm 100mW); then develop it with a 1% NaOH aqueous solution at 25℃, wash it with ultrapure water, and air dry it. Finally, bake it at 220℃ for 30min, and evaluate the obtained graphics.

[0230] Table 4 Polymerization experimental results of compounds A1, A4, A7, A8, A10, A12, A20, A22, A23, A25, A27, A30 as photoinitiators

[0231]

[0232]

[0233] The polymerization results are shown in Table 4. The triarylboron organic compounds used in Table 4 can effectively initiate photocuring. Taking the coating obtained from compound A-1 as an example, Figure 3 As shown in A in the figure, the cured pattern is colorless, transparent and odorless under natural light, and there is no abnormality when viewed visually. Under dark field UV light, the cured coating pattern can be clearly observed, the board pattern is complete, and there is almost no residue in the unexposed part (such as Figure 3 (as shown in B in the figure).

[0234] It can be seen from the above embodiments that the present invention provides a type of triaryl boron organic compound, whose structure is shown in general formula I, with methyl-substituted triphenylborane as the electron acceptor unit and electron-rich D group as the electron donor unit. The triaryl boron compound provided by the present invention has excellent light and thermal stability and can be stored and transported under daily conditions; its absorption wavelength can be extended to the visible light region, and it has a good molar extinction coefficient in the visible light region. The triaryl boron compound provided by the present invention can be used as a single-component photoinitiator and added to an ordinary photocuring system. The system after addition can effectively initiate photocuring under a light source in the visible light region, and form a pure organic photocurable coating that can emit light under visible light, which has a wide range of uses, including but not limited to photoresist, three-dimensional printing, anti-counterfeiting and other fields.

[0235] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A triarylboron organic compound, characterized in that: It has the general structural formula shown in Formula I: General formula Ⅰ; The structure of the D group in the general formula I is shown in formula a, formula b, formula c, formula d or formula e: Formula a, Formula b, Formula c, Formula d, Formula e; In formula a, formula b, formula c, formula d, and formula e, R is a hydrogen atom, C 1-3 Alkoxy, halogen, hydroxy, nitro, cyano, unsubstituted or substituted C 1-20 Straight or branched alkyl, C 3-20 cycloalkyl, alkyl-substituted cycloalkyl, phenyl, C 4-20 alkyl substituted phenyl or biphenyl; the substituted C 1-20 The substituents of the straight chain or branched alkyl group are cycloalkyl, hydroxyl and C 1-3 One or more of the alkoxy groups; the cycloalkyl-substituted C 1-20 The total number of carbon atoms in a straight or branched alkyl group is C 4-20 The total number of carbon atoms in the alkyl-substituted cycloalkyl group is C 4-20 .

2. The triarylboron organic compound according to claim 1, characterized in that In formula a, R is a hydrogen atom, a halogen, a hydroxyl group, a C 1-3 Alkoxy, unsubstituted or substituted C 1-20 A straight or branched alkyl group, a phenyl group or a biphenyl group; In formula b, R is a hydrogen atom, a halogen, or a C 1-3 Alkoxy or unsubstituted or substituted C 1-20 A straight chain or branched alkyl group; In formula c, R is a hydrogen atom, a halogen, a hydroxyl group, or a C 1-3 Alkoxy, unsubstituted or substituted C 1-20 A straight or branched alkyl or phenyl group; In formula d, R is a hydrogen atom, a halogen, a hydroxyl group, a C 1-3 Alkoxy or unsubstituted or substituted C 1-20 A straight chain or branched alkyl group; In formula e, R is a hydrogen atom, a halogen, a hydroxyl group, a C 1-3 Alkoxy, unsubstituted or substituted C 1-20 A straight chain or branched chain alkyl or phenyl group.

3. The triarylboron organic compound according to claim 1 or 2, characterized in that The D group has any one of the following structures: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。 4. The method for preparing a triarylboron organic compound according to any one of claims 1 to 3, characterized in that: The following steps are involved: A compound of formula 2, a DH compound, an organic palladium catalyst and an acid-binding agent are subjected to a Buchwald-Hartwig coupling reaction in an organic solvent to obtain a triarylboron organic compound of formula I; the D group in the DH compound is the same as the D group in the triarylboron organic compound of formula I; Formula 2.

5. The preparation method according to claim 4, characterized in that: The preparation method of the compound of the structure shown in Formula 2 comprises the following steps: Di(trimethylphenyl)boron fluoride, 2,5-dibromo-m-xylene and n-butyl lithium are subjected to a nucleophilic substitution reaction in an organic solvent to obtain a compound shown in formula 2.

6. Use of the triaryl boron organic compound according to any one of claims 1 to 3 or the triaryl boron organic compound prepared by the preparation method according to claim 4 or 5 as an organic photoinitiator.

7. A photocurable material, characterized in that: The raw materials of the photocurable material include a prepolymerized photosensitive resin, an active monomer and a photoinitiator; the photoinitiator is a triaryl boron organic compound as described in any one of claims 1 to 3 or a triaryl boron organic compound prepared by the preparation method as described in claim 4 or 5.

8. The photocurable material according to claim 7, characterized in that: The prepolymerized photosensitive resin is a resin having a vinyl group; and the active monomer is a monomer having a vinyl group.

9. The photocurable material according to claim 7 or 8, characterized in that: The raw materials of the photocurable material further include one or more of a colorant, a solvent, a photocrosslinking agent, a photosensitizer, an antioxidant, a surfactant, a curing accelerator and a thermal polymerization inhibitor.

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