Triarylamine-based compound, preparation method thereof, photocuring adhesive and application

Abstract

The invention discloses a compound based on triarylamine, a preparation method of the compound, a photocuring adhesive and application of the photocuring adhesive. The triarylated amine-based compound comprises a compound which takes a bis-triarylated amine structural unit as a core structure and takes an organic group containing a carbon-carbon double bond as a side chain structure. The triarylamine-based compound has the characteristics of wide band gap, high light transmittance, high refractive index and high stability, the triarylamine-based compound containing carbon-carbon double bonds can be cured in a thermal initiation or photo-initiation mode to prepare a coating, and the triarylamine-based compound has the advantage of high efficiency and polymerizability.

Description

Technical Field

[0001] This application belongs to the field of optical materials technology, specifically relating to a triarylamine-based compound, its preparation method, photocurable adhesive, and applications. Background Technology

[0002] In recent years, resin-based dispersions prepared by combining inorganic nanoparticle dispersions with transparent resins or films have found excellent applications in the optical field, such as zirconia nanoparticles and silica nanoparticles. Zirconia resin-based dispersions are used to prepare optical films such as brightness-enhancing films and anti-reflective films, which can be used in LCD displays to increase screen brightness and clarity, or in other optical devices to obtain high-refractive-index films. For these applications, not only are high refractive indices and low viscosity required, but good compatibility with resins in downstream applications is also essential to create UV-curable adhesives that can be uniformly coated onto the surface of the optical film. However, the incompatibility of inorganic nanoparticles such as zirconia or titanium dioxide with resins leads to inhomogeneity in resin dispersions containing inorganic nanoparticles. Furthermore, the synthesis of inorganic oxide nanoparticles is difficult to control, often resulting in a large number of nanoparticles with poor dispersion and complex crystalline phase structures, all of which severely affect the use and long-term stability of optical films or resins, thus limiting the application potential of these materials. Therefore, in order to meet market demand, it is crucial to prepare high-refractive-index polymer units with all-organic or extremely low inorganic nanoparticle content, as well as UV-curable adhesives with good compatibility and high light transmittance.

[0003] Although some all-polymer optical adhesives have been successfully prepared, most of them suffer from problems such as low refractive index and difficulty in UV curing, which affects their performance when applied to downstream display fields. For example, the refractive index of polymers cured from monomers such as acrylic acid and alkenyl carbazole rarely exceeds 1.7.

[0004] Therefore, there is a need to develop an all-organic UV-curable adhesive with simple process, coordinated indicators in the system, good compatibility, stability and high refractive index, which is of great significance for subsequent production. In view of this, this application is hereby submitted. Summary of the Invention

[0005] Therefore, the technical problem to be solved by this application is to overcome the above-mentioned defects in the prior art, and aims to provide a triarylamine-based compound that has the advantages of wide bandgap, high transmittance, high refractive index and high stability.

[0006] In a first aspect, this application provides a triarylamine-based compound, which includes compounds having a bistriarylamine structural unit as the core structure and an organic group containing a carbon-carbon double bond as the side chain structure.

[0007] The compounds provided in this application contain a conjugated system with a bis(triarylamine) structure as the core structure and an electron-rich conjugated group of the triarylamine as the donor unit, forming a multi-conjugated structure with strong donor properties. At the same time, corresponding curable structural units containing carbon-carbon double bonds are constructed, so that the triarylamine-based compounds have the advantages of wide bandgap, high transmittance in the visible light region, high refractive index, high stability and high efficiency photopolymerization.

[0008] In any implementation, the core structure includes the structure shown in Formula I.

[0009]

[0010] Among them, Ar 10 Ar 21 Ar 22 Ar 23 and Ar 24 Each independently includes substituted or unsubstituted C 6～50 aryl, substituted or unsubstituted C 2～50 At least one of the heteroarylene groups. Indicates the binding site;

[0011] The side chain structure includes at least one of the structures shown in Formula II-1, Formula II-2, Formula II-3, and Formula II-4.

[0012]

[0013] Among them, R 21 R 22 R 23 and R 24 Each independently includes substituted or unsubstituted C 1～20 alkoxy, substituted or unsubstituted C 6～20 At least one of the heteroaryl groups;

[0014] a1, a2, a3 and a4 are each independently 0 or integers from 1 to 12, and a1, a2, a3 and a4 are not all 0 at the same time;

[0015] X1, X2, X3, and X4 each independently include at least one of hydrogen, vinyl, α-methylvinyl, acryloyl, α-methacryloyl, vinylphenyl, and α-methylvinylphenyl, and X1, X2, X3, and X4 are not all hydrogen at the same time, ------ indicates a binding site.

[0016] In any embodiment, the triarylamine-based compound includes compounds with the structure shown in Formula III.

[0017]

[0018] Among them, Ar 10 Ar 21 Ar 22 Ar 23 and Ar 24 Each independently includes substituted or unsubstituted C 6～50 aryl, substituted or unsubstituted C 2～50 At least one of the heteroarylene groups;

[0019] R 21 R 22 R 23 and R 24 Each independently includes substituted or unsubstituted C 1～20 alkoxy, substituted or unsubstituted C 6～20 At least one of the heteroaryl groups;

[0020] a1, a2, a3, and a4 are each independently 0 or integers from 1 to 12, and a1, a2, a3, and a4 are not all 0 at the same time;

[0021] X1, X2, X3 and X4 each independently include at least one of hydrogen, vinyl, α-methylvinyl, acryloyl, α-methacryloyl, vinylphenyl, α-methylvinylphenyl, and not all of X1, X2, X3 and X4 are hydrogen at the same time.

[0022] A second aspect of this application provides a method for preparing a triarylamine-based compound, comprising the following steps:

[0023] Under reactivity conditions, a first raw material comprising a first reactant and a second reactant undergoes a first reaction to prepare a first intermediate;

[0024] Under reactive conditions, the first intermediate is subjected to a hydroxylation reaction to prepare the second intermediate;

[0025] Under reactive conditions, the second intermediate is first subjected to a chain extension reaction, followed by an alkenylation reaction, to prepare the triarylamine-based compound;

[0026] The first reactant includes a compound with the structure shown in Formula IV.

[0027]

[0028] Ar 22 and Ar 23 Each independently includes substituted or unsubstituted C 6～50 aryl, substituted or unsubstituted C 2～50At least one of the heteroarylene groups, Y2 and Y3 each independently include at least one of hydrogen and methoxy groups, and Y2 and Y3 are not both hydrogen;

[0029] The first reactant includes at least one of the compounds with the structure shown in Formula V and the compounds with the structure shown in Formula VI.

[0030]

[0031] Ar 20 Ar 30 Ar 21 and Ar 24 Each independently includes substituted or unsubstituted C 6～50 aryl, substituted or unsubstituted C 2～50 At least one of the heteroarylene groups, Y1 and Y4 each independently include at least one of hydrogen and methoxy groups, and Y5 and Y6 each independently include at least one of F, Br, and Cl.

[0032] In any embodiment, the chain extension reaction includes:

[0033] Under reactivity conditions, the second intermediate is reacted with a compound having the structure shown in Formula VIII.

[0034] Y 10 ——R 10 -OH formula VIII,

[0035] R10 includes at least one of substituted or unsubstituted C1-10 alkylene groups, and Y10 includes at least one of bromine, fluorine, and chlorine.

[0036] In any embodiment, the alkenylation reaction includes:

[0037] Under reactivity conditions, the product of the chain extension reaction is reacted with a third reactant containing a double bond in the second reaction to prepare the triarylamine-based compound; wherein the third reactant containing a double bond includes a compound with the structure shown in Formula VII.

[0038]

[0039] R 41 It includes at least one of substituted or unsubstituted acyl chloride group and substituted or unsubstituted benzoic acid group.

[0040] A third aspect of this application provides a photocurable adhesive, the photocurable adhesive comprising a triarylamine-based compound as described in any embodiment or a triarylamine-based compound prepared by the preparation method described in any embodiment.

[0041] A fourth aspect of this application provides the application of a photocurable adhesive in photoresist, lens coating, diffractive waveguide, or nanoimprint in any embodiment.

[0042] The technical solution of this application has the following beneficial effects:

[0043] The triarylamine-based compound provided in this application has a structure comprising two parts: one part is a conjugated rigid unit containing a bis(triarylamine) core framework, which exhibits a high refractive index in the aggregated state; the other part consists of flexible side groups containing terminal carbon-carbon double bonds, which can be cured by thermal or UV light initiation. This triarylamine-based compound possesses characteristics such as a wide bandgap, high transmittance in the visible light region, high refractive index, high stability, and high polymerizability. Furthermore, the compound exhibits low viscosity, which is beneficial for subsequent processing.

[0044] The method for preparing triarylamine-based compounds provided in this application has readily available starting materials, mild reaction conditions, and simple operation steps, which is conducive to the large-scale production of triarylamine-based compounds.

[0045] The UV-curable adhesive provided in this application, through appropriate non-conjugated functionalization (selection of flexible side groups), can be used to appropriately alkenylate compounds containing conjugated rigid units with a triarylamine core framework, thereby obtaining a variety of UV photopolymerizable monomers with high refractive indices and acrylic and vinylphenyl terminal groups. This UV-curable adhesive has the advantages of low viscosity and high refractive index, and the coatings prepared from it exhibit excellent light transmittance, making it widely applicable in fields such as nanoimprint lithography, photoresists, and high-performance optical coatings. Detailed Implementation

[0046] The following detailed description discloses the triarylamine-based compounds, their preparation methods, photocurable adhesives, and application embodiments of this application. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of practically identical structures may be omitted. This is to avoid unnecessarily lengthy descriptions and to facilitate understanding by those skilled in the art. Furthermore, the following description is provided to enable those skilled in the art to fully understand this application and is not intended to limit the subject matter of the claims. Any product identical or similar to this application, derived by any person based on the teachings of this application or by combining features of this application with other prior art, falls within the protection scope of this application.

[0047] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, the numerical range "ab" represents a shortened representation of any combination of real numbers from a to b, where a and b are real numbers. Similarly, the numerical range "0-7" indicates that all real numbers between "0" and "7" have been listed in this document; "0-7" is simply a shortened representation of these numerical combinations. Furthermore, when describing an integer with a parameter ≥ 3, it is equivalent to disclosing that the parameter is, for example, an integer such as 3, 4, 5, 6, 7, 8, 9, 10, 11, etc.

[0048] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0049] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0050] Unless otherwise specified, all steps of this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (1) and (2), indicating that the method may include steps (1) and (2) performed sequentially, or it may include steps (2) and (1) performed sequentially. For example, the mention that the method may also include step (3) indicates that step (3) may be added to the method in any order. For example, the method may include steps (1), (2) and (3), or it may include steps (1), (3) and (2), or it may include steps (3), (1) and (2), etc.

[0051] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0052] Unless otherwise specified, the term "or" is inclusive in this application. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0053] Terminology Explanation:

[0054] In this specification, unless otherwise defined, "substituted" means that at least one hydrogen atom of a substituent or compound is replaced by a deuterium, halogen, cyano, substituted or unsubstituted C atom. 1-24 Alkyl, C 3-30 cycloalkyl, C 6-30 Aryl, C 2-30 heteroaryl groups or combinations thereof.

[0055] In this specification, unless otherwise defined, “heterogeneous” means including one or two heteroatoms selected from N, O, S, B, P and Si, and the remaining carbon in a functional group.

[0056] In this specification, unless otherwise defined, "alkyl" refers to an aliphatic hydrocarbon group. An alkyl group can be C10, C20, C30, C40, C50, C60, C7 ... 1-30 Alkyl group. More specifically, the alkyl group can be C10. 1-20 Alkyl or C 1-10 Alkyl group. For example, C 1-4 The alkyl group may have 1 to 4 carbon atoms in the alkyl chain and may be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

[0057] Specific examples of alkyl groups can be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

[0058] In this specification, "aryl" refers to a group comprising at least one aromatic hydrocarbon moiety, wherein all elements of the aromatic hydrocarbon moiety have conjugated p-orbitals, such as phenyl, naphthyl, etc., and two or more aromatic hydrocarbon moietyes may be linked by σ bonds and may be, for example, biphenyl, terphenyl, tetraphenyl, etc., or two or more aromatic hydrocarbon moietyes may be directly or indirectly fused to provide a non-aromatic fused ring. For example, it may be fluorenyl. Aryl groups may include monocyclic, polycyclic, or fused-ring polycyclic (i.e., rings sharing adjacent carbon atom pairs) functional groups.

[0059] In this specification, "heterocyclic group" is a general concept of heteroaryl and may include at least one heteroatom selected from N, O, S, P, and Si in place of carbon (C) in cyclic compounds such as aryl, cycloalkyl, their fused rings, or combinations thereof. When the heterocyclic group is a fused ring, the entire ring or each ring of the heterocyclic group may contain one or more heteroatoms. For example, "heteroaryl" refers to an aryl group that includes at least one heteroatom selected from N, O, S, P, and Si. Two or more heteroaryl groups are directly connected by σ bonds, or when the heteroaryl group contains two or more rings, the two or more rings may be fused. When the heteroaryl group is a fused ring, each ring may contain 1 to 3 heteroatoms. Specific examples of heterocyclic groups may be pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiopheneyl or combinations thereof, but are not limited thereto.

[0060] This application proposes a triarylamine-based compound, which includes compounds with a core structure of a bistriarylamine structural unit and a side chain structure of an organic group containing a carbon-carbon double bond.

[0061] The triarylamine-based compound provided in this application contains a conjugated system with a bis(triarylamine) group as the core structure and uses the electron-rich conjugated group of the triarylamine as the donor unit to form a multi-conjugated structure with strong donor properties. Simultaneously, it constructs corresponding curable structural units containing carbon-carbon double bonds, giving the triarylamine-based compound advantages such as wide bandgap, high transmittance in the visible light region, high refractive index, high stability, and efficient photopolymerization. Research has shown that this triarylamine-based compound has low viscosity and high refractive index characteristics, which is not only beneficial for preparing high-refractive-index all-organic photocurable adhesives but also provides a wide processing window, thus broadening its applications in the optical field.

[0062] In some implementations, the core structure includes the structure shown in Formula I.

[0063]

[0064] Among them, Ar 10 Ar 21 Ar 22 Ar 23 and Ar 24 Each independently includes substituted or unsubstituted C 6～50 aryl, substituted or unsubstituted C 2～50 At least one of the heteroarylene groups. Indicates the binding site.

[0065] In some embodiments, the side chain structure includes at least one of the structures shown in Formula II-1, Formula II-2, Formula II-3, and Formula II-4.

[0066]

[0067] Among them, R 21 R 22 R 23 and R 24 Each independently includes substituted or unsubstituted C 1～20 alkoxy, substituted or unsubstituted C 6～20 At least one of the heteroaryl groups;

[0068] a1, a2, a3 and a4 are each independently 0 or integers from 1 to 12, and a1, a2, a3 and a4 are not all 0 at the same time;

[0069] X1, X2, X3, and X4 each independently include at least one of hydrogen, vinyl, α-methylvinyl, acryloyl, α-methacryloyl, vinylphenyl, and α-methylvinylphenyl, and X1, X2, X3, and X4 are not all hydrogen. Indicates the binding site.

[0070] In this application, the non-zero side chain structures in a1, a2, a3, and a4 correspond to X1, X2, X3, or X4 that are not hydrogen. Research has found that X1, X2, X3, or X4 are not directly connected to the bis(triarylamine) structural unit, but rather act as a bridge between X1, X2, X3, or X4 and the bis(triarylamine) structural unit through alkoxy or oxygen-containing aromatic groups. This gives the triarylamine-based compound the characteristics of low viscosity, high solubility, and high refractive index, and the coating prepared from it has excellent light transmittance, which is beneficial for the preparation of high refractive index all-organic photocurable adhesives.

[0071] In some embodiments, the triarylamine-based compounds include compounds with the structure shown in Formula III.

[0072]

[0073] Among them, Ar 10 Ar 21 Ar 22 Ar 23 and Ar 24 Each independently includes substituted or unsubstituted C 6～50 aryl, substituted or unsubstituted C 2～50 At least one of the heteroarylene groups;

[0074] R 21 R 22R 23 and R 24 Each independently includes substituted or unsubstituted C 1～20 alkoxy, substituted or unsubstituted C 6～20 At least one of the heteroaryl groups;

[0075] a1, a2, a3, and a4 are each independently 0 or integers from 1 to 12, and a1, a2, a3, and a4 are not all 0 at the same time;

[0076] X1, X2, X3 and X4 each independently include at least one of hydrogen, vinyl, α-methylvinyl, acryloyl, α-methacryloyl, vinylphenyl, α-methylvinylphenyl, and not all of X1, X2, X3 and X4 are hydrogen at the same time.

[0077] In some implementations, Ar 10 Ar 21 Ar22, Ar23, and Ar24 each independently include at least one of the following: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted thiophene, substituted or unsubstituted thiazolyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted oxadiazolyl, phthalimide, substituted or unsubstituted benzothiophene, substituted or unsubstituted benzofuranyl, substituted or unsubstituted naphtho-(benzofuranyl), substituted or unsubstituted naphthofuranyl, substituted or unsubstituted indolocarbazolyl, substituted or unsubstituted triphenylene, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, and substituted or unsubstituted quinazolinyl.

[0078] In some implementations, Ar 10 Ar 21 Ar 22 Ar 23 and Ar 24 Each of these can be independently represented by the following formulas and their derivatives:

[0079]

[0080] Among them, Z1, Z2, Z3 and Z4 each independently include hydrogen, deuterium, F, Cl, CN and C. 1～24 Alkyl, C 1～24 At least one of alkoxy, phenyl, biphenyl, naphthyl, triphenylene, anthracene, pyrene, and phenanthrene, wherein d1 and d2 are each independently 0 or integers from 1 to 3. Indicates the binding site.

[0081] In this paper, the term "binding site" refers to a group site that can form a covalent bond with other groups.

[0082] In some implementations, Ar 10 Ar 21 Ar 22 Ar 23 and Ar 24 Each of these can be independently represented by the following formulas and their derivatives:

[0083]

[0084] in, Indicates the connection site; T1 and T2 each independently include C 1～24 At least one of the following: alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted phenoxazine group, or substituted or unsubstituted phenothiazine group.

[0085] In this paper, the term "linking site" refers to any group site that can form a covalent bond with other groups, and is not limited to a specific group site.

[0086] In some implementations, the sidechain structure includes At least one of them, ------ represents the binding site, and m and n are each independent integers from 1 to 24.

[0087] In some embodiments, X1, X2, X3 and X4 each independently include at least one of hydrogen, vinyl, α-methylvinyl, acryloyl, α-methacryloyl, vinylphenyl, α-methylvinylphenyl, and at least two of X1, X2, X3 and X4 are not simultaneously hydrogen.

[0088] In some embodiments, X1, X2, X3 and X4 each independently include at least one of hydrogen, vinyl, α-methylvinyl, acryloyl, α-methacryloyl, vinylphenyl, α-methylvinylphenyl, and at least three of X1, X2, X3 and X4 are not hydrogen at the same time.

[0089] In some embodiments, X1, X2, X3 and X4 each independently include at least one of vinyl, α-methylvinyl, acryloyl, α-methacryloyl, vinylphenyl, and α-methylvinylphenyl.

[0090] Multifunctional triarylamine-based compounds have more active sites, allowing for greater cross-linking with monomers in photocurable adhesives and improving the strength of the resulting coatings.

[0091] This application also provides a method for preparing a triarylamine-based compound, comprising the following steps:

[0092] Under reactivity conditions, a first raw material comprising a first reactant and a second reactant undergoes a first reaction to prepare a first intermediate;

[0093] Under reactive conditions, the first intermediate is hydroxylated to prepare the second intermediate;

[0094] Under reactive conditions, the second intermediate is first subjected to a chain extension reaction, followed by an alkenylation reaction, to prepare a triarylamine-based compound;

[0095] The first reactant includes a compound with the structure shown in Formula IV.

[0096]

[0097] Ar 22 and Ar 23 Each independently includes substituted or unsubstituted C 6～50 aryl, substituted or unsubstituted C 2～50 At least one of the heteroarylene groups, Y2 and Y3 each independently include at least one of hydrogen and methoxy groups, and Y2 and Y3 are not both hydrogen;

[0098] The first reactant includes at least one of the compounds with the structure shown in Formula V and the compounds with the structure shown in Formula VI.

[0099]

[0100] Ar 20 Ar 30 Ar 21 and Ar 24 Each independently includes substituted or unsubstituted C 6～50 aryl, substituted or unsubstituted C 2～50 At least one of the heteroarylene groups, Y1 and Y4 each independently include at least one of hydrogen and methoxy groups, and Y5 and Y6 each independently include at least one of F, Br, and Cl.

[0101] In some embodiments, Y2 comprises a methoxy group, and Y3 comprises hydrogen. In some embodiments, Y2 comprises hydrogen, and Y3 comprises a methoxy group. In some embodiments, Y1 comprises a methoxy group, and Y4 comprises hydrogen. In some embodiments, Y1 comprises a methoxy group, and Y4 comprises a methoxy group. In some embodiments, Y5 comprises bromine. In some embodiments, Y6 comprises fluorine.

[0102] In some embodiments, the chain extension reaction includes:

[0103] Under reactivity conditions, the second intermediate is reacted with a compound having the structure shown in Formula VIII.

[0104] Y10 ——R 10 —OH Formula VIII,

[0105] R 10 Including substituted or unsubstituted C 1-10 At least one of the alkylene groups, Y 10 It includes at least one of bromine, fluorine, and chlorine.

[0106] In some implementations, R 10 Including -CH2CH2CH2CH2-. In some implementations, R 10 Including -CH2CH2CH2-. In some implementations, R 10 Including -CH2CH2-. In some implementations, R 10 Including -CH2CH2CH2CH2CH2-. In some embodiments, Y 10 Includes bromine. In some embodiments, Y 10 Including chlorine.

[0107] In some embodiments, the alkenylation reaction includes:

[0108] Under reactive conditions, the product of the chain extension reaction is reacted with a third reactant containing a double bond in a second reaction to prepare a triarylamine-based compound; wherein the third reactant containing a double bond includes a compound with the structure shown in Formula VII.

[0109]

[0110] R 41 It includes at least one of substituted or unsubstituted acyl chloride group and substituted or unsubstituted benzoic acid group.

[0111] In some implementations, R 41 Includes an acyl chloride group. In some embodiments, R 41 Including benzoic acid groups.

[0112] In some embodiments, the hydroxylating agent includes at least one of boron tribromide, boron trichloride, aluminum trichloride, or pyridine hydrochloride.

[0113] In some embodiments, the hydroxylation solvent includes at least one selected from dichloromethane, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, cyclohexane, n-hexane, or petroleum ether.

[0114] This application also provides a photocurable adhesive, which includes triarylamine-based compounds in some embodiments or triarylamine-based compounds prepared by the preparation methods in some embodiments.

[0115] This application also provides some embodiments of the use of photocurable adhesives in photoresists, lens coatings, diffractive waveguides, or nanoimprints.

[0116] Example

[0117] The following embodiments are provided to better understand this application and are not limited to the preferred embodiments described herein. They do not constitute a limitation on the content and scope of protection of this application. Any product that is the same as or similar to this application, derived by anyone under the guidance of this application or by combining features of this application with other prior art, falls within the scope of protection of this application.

[0118] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0119] I. Preparation Method

[0120] Example 1

[0121]

[0122] Preparation of compound M1 based on triarylamine:

[0123] Compound M1-1, compound M1-2, sodium tert-butoxide, 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (Sphos), and Pd2dba3 were weighed in a molar ratio of 1:1:2:0.02:0.01 and placed in a three-necked flask. 200 ml of anhydrous toluene was added, and the mixture was purged with nitrogen for 15 min. The reaction was then carried out at 120 °C for 8 h under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled to room temperature, extracted with ethyl acetate, and the organic phase was concentrated and subjected to column chromatography to obtain compound M1-3.

[0124] Compound M1-3 was dissolved in dry dichloromethane (DCM), and the solution was cooled to -45°C under a nitrogen atmosphere. A solution of BBr3 (in a molar ratio of 1:4) in dichloromethane (DCM) was added dropwise using a syringe. After the addition was complete, the reaction mixture was allowed to react at 40°C for 18 hours. After the reaction was complete, the reaction solution was poured into ice water, extracted, dried, and then subjected to ethanol slurrying and column chromatography to obtain M1-4.

[0125] Compound M1-4 was dissolved in tetrahydrofuran, followed by the addition of KOH, KI, and 4-bromo-1-butanol (the molar ratio of M1-4, KOH, KI, and 4-bromo-1-butanol was 1:4:0.12:1.5). The mixture was refluxed at 85°C for 10 h under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled, extracted with ethyl acetate, dried, and then slurried with ethanol to obtain M1-5.

[0126] Compound M1-5 was dissolved in dry dichloromethane (DCM, 40 mL), and triethylamine (M1-5 to triethylamine molar ratio 1:2) was added. The mixture was cooled to -5°C under a nitrogen atmosphere, and acryloyl chloride (M1-5 to acryloyl chloride molar ratio 8:5) was added dropwise using a syringe. After the addition was complete, the reaction mixture was allowed to react at low temperature for 5 h. After the reaction was complete, the reaction solution was poured into ice water, extracted, dried, and then rapidly purified by a neutral alumina column to obtain compound M1 based on a triarylamine. Elemental analysis: (C 80 H 60 Theoretical N₂O₃ values: C, 87.56; H, 5.51; N, 2.55; O, 4.37; Measured values: C, 89.91; H, 5.82; N, 2.62; HR-MS (ESI-[M+1]) + (m / z): Theoretical value: 1096.46, measured value: 1096.52.

[0127] The reaction equation for preparing compound M1 based on triarylamine is as follows:

[0128]

[0129] Example 2

[0130]

[0131] Preparation of compound M2 based on triarylamine:

[0132] Compounds M2-1, M1-2, sodium tert-butoxide, 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl (Sphos), and Pd2dba3 were weighed in a molar ratio of 1:1:2:0.02:0.01 and placed in a three-necked flask. 200 ml of anhydrous toluene was added, and the mixture was purged with nitrogen for 15 min. The reaction was then carried out at 130 °C for 8 hours under nitrogen protection. After the reaction was completed, the mixture was cooled to room temperature, extracted with ethyl acetate, and the organic phase was concentrated and subjected to column chromatography to obtain compound M2-2.

[0133] The above compound M2-2 was dissolved in dry dichloromethane (DCM), and the mixture was cooled to -45°C under nitrogen protection. A DCM solution of BBr3 (M2-2 to BBr3 in a molar ratio of 1:4) was added dropwise using a syringe. After the addition was complete, the mixture was reacted at 40°C for 18 hours. After the reaction was complete, the reaction solution was poured into ice water, extracted, dried, and then subjected to ethanol slurrying and column chromatography to obtain M2-3.

[0134] Compound M2-3 was dissolved in tetrahydrofuran, followed by the addition of KOH, KI, and 4-bromo-1-butanol (the molar ratio of M2-3, KOH, KI, and 4-bromo-1-butanol was 1:4:0.12:1.5). The mixture was refluxed at 85°C for 10 h under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled, extracted with ethyl acetate, dried, and then slurried with ethanol to obtain M2-4.

[0135] Compound M2-4 was dissolved in dry dichloromethane (DCM, 40 mL), and triethylamine (molecular ratio of M2-4 to triethylamine 1:2) was added. The mixture was cooled to -5°C under a nitrogen atmosphere, and acryloyl chloride (molecular ratio of M2-4 to acryloyl chloride 8:5) was added dropwise using a syringe. After the addition was complete, the reaction mixture was allowed to react at low temperature for 5 h. After the reaction was complete, the reaction solution was poured into ice water, extracted, dried, and then rapidly purified by a neutral alumina column to obtain compound M2 based on a triarylamine. Elemental analysis: (C 67 H 50 Theoretical values ​​for N₂O₃S: C, 83.55; H, 5.23; N, 2.91; O, 4.98; S, 3.33; Measured values: C, 83.62; H, 5.37; N, 2.94; S, 3.31; HR-MS (ESI-[M+1]) + (m / z): Theoretical value: 962.35; Measured value: 963.44.

[0136] The reaction equation for preparing the triarylamine-based compound M2 is as follows:

[0137]

[0138] Example 3

[0139]

[0140] Preparation of compound M3 based on triarylamine:

[0141] Compounds M3-1, M3-2, sodium tert-butoxide, Sphos, and Pd2dba3 were weighed in a molar ratio of 1:1:2:0.02:0.01 and placed in a three-necked flask. 200 ml of anhydrous toluene was added, and the mixture was purged with nitrogen for 15 min. The reaction was then carried out at 130 °C for 8 hours under nitrogen protection. After the reaction was completed, the mixture was cooled to room temperature, extracted with ethyl acetate, and the organic phase was concentrated and subjected to column chromatography to obtain compound M3-3.

[0142] The above compound M3-3 was dissolved in dry dichloromethane (DCM), and the mixture was cooled to -45°C under nitrogen protection. A DCM solution of BBr3 (M3-3 to BBr3 in a molar ratio of 1:4) was added dropwise using a syringe. After the addition was complete, the mixture was reacted at 40°C for 18 hours. After the reaction was complete, the reaction solution was poured into ice water, extracted, dried, and then subjected to ethanol slurrying and column chromatography to obtain M3-4.

[0143] Compound M3-4 was dissolved in tetrahydrofuran, followed by the addition of KOH, KI, and 4-bromo-1-butanol (the molar ratio of M3-4, KOH, KI, and 4-bromo-1-butanol was 1:4:0.12:1.5). The mixture was refluxed at 85°C for 10 h under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled, extracted with ethyl acetate, dried, and then slurried with ethanol to obtain M3-5.

[0144] Compound M3-5 was dissolved in dry dichloromethane (DCM, 40 mL), and triethylamine (molecular ratio of M3-5 to triethylamine 1:2) was added. The mixture was cooled to -5°C under a nitrogen atmosphere, and acryloyl chloride (molecular ratio of M3-5 to acryloyl chloride 8:5) was added dropwise using a syringe. After the addition was complete, the reaction mixture was allowed to react at low temperature for 5 h. After the reaction was complete, the reaction solution was poured into ice water, extracted, dried, and then rapidly purified by a neutral alumina column to obtain compound M3, which is based on a triarylamine. Elemental analysis: (C 97 H 92 Theoretical N₂O₄ values: C, 86.31; H, 6.87; N, 2.08; O, 4.74; Measured values: C, 86.42; H, 6.97; N, 2.09; HR-MS (ESI-[M+1]) + (m / z): Theoretical value: 1348.71; Measured value: 1349.81.

[0145] The reaction equation for preparing compound M3 based on triarylamines is as follows:

[0146]

[0147] Example 4

[0148]

[0149] Preparation of compound M4 based on triarylamine:

[0150] Compound M3-5 from Example 3 was dissolved in dry dichloromethane (DCM, 40 mL), and dicyclohexylcarbodiimide (M3-5 to DCC molar ratio 1:200) and N,N-dimethylaminopyridine (M3-5 to DMAP molar ratio 1:30) were added. The mixture was cooled to -5°C under nitrogen protection, and a dichloromethane solution of 4-vinylbenzoic acid (M3-5 to 4-vinylbenzoic acid molar ratio 2:1) was added dropwise using a syringe. After the addition was complete, the reaction was carried out at 25°C for 8 hours. After the reaction was complete, the solution was directly filtered, and the solution was rapidly purified by neutral alumina column chromatography to obtain compound M4, which is based on a triarylamine. Elemental analysis: (C 99 H 88 Theoretical N₂O₃ values: C, 87.83; H, 6.55; N, 2.07; O, 3.55; Measured values: C, 87.91; H, 6.57; N, 2.09; HR-MS (ESI-[M+1]) + (m / z): Theoretical value: 1352.68; Measured value: 1368.65.

[0151] The reaction equation for preparing compound M4 based on triarylamines is as follows:

[0152]

[0153] Example 5

[0154]

[0155] Preparation of compound M5 based on triarylamine:

[0156] Compounds M5-1, M5-2, sodium tert-butoxide, Sphos, and Pd2dba3 were weighed in a molar ratio of 1:1:2:0.02:0.01 and placed in a three-necked flask. 200 ml of anhydrous toluene was added, and the mixture was purged with nitrogen for 15 min. The reaction was then carried out at 130 °C for 8 hours under nitrogen protection. After the reaction was completed, the mixture was cooled to room temperature, extracted with ethyl acetate, and the organic phase was concentrated and subjected to column chromatography to obtain compound M5-3.

[0157] The above compound M5-3 was dissolved in dry dichloromethane (DCM), and the mixture was cooled to -45°C under nitrogen protection. A DCM solution of BBr3 (M5-3 to BBr3 in a molar ratio of 1:8) was added dropwise using a syringe. After the addition was complete, the mixture was reacted at 40°C for 18 hours. After the reaction was complete, the reaction solution was poured into ice water, extracted, dried, and then subjected to ethanol slurrying and column chromatography to obtain M5-4.

[0158] The above compound M5-4 was dissolved in tetrahydrofuran, followed by the addition of KOH, KI, and 4-bromo-1-butanol (the molar ratio of M5-4, KOH, KI, and 4-bromo-1-butanol was 1:4:0.12:3). The mixture was refluxed at 85°C for 10 h under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled, extracted with ethyl acetate, dried, and then slurried with ethanol to obtain M5-5.

[0159] Compound M5-5 was dissolved in dry dichloromethane (DCM, 40 mL), and triethylamine (molecular ratio of M5-5 to triethylamine 1:2) was added. The mixture was cooled to -5°C under a nitrogen atmosphere, and acryloyl chloride (molecular ratio of M5-5 to acryloyl chloride 8:5) was added dropwise using a syringe. After the addition was complete, the reaction mixture was allowed to react at low temperature for 5 h. After the reaction was complete, the reaction solution was poured into ice water, extracted, dried, and then rapidly purified by a neutral alumina column to obtain compound M5, which is based on a triarylamine. Elemental analysis: (C 87 H 70 Theoretical N₂O₆ values: C, 84.30; H, 5.69; N, 2.26; O, 7.74; Measured values: C, 84.43; H, 5.73; N, 2.29; HR-MS (ESI-[M+1]) + (m / z): Theoretical value: 1338.52; Measured value: 1239.52.

[0160] The reaction equation for preparing compound M5, which is based on a triarylamine, is as follows:

[0161]

[0162] Example 6

[0163]

[0164] Preparation of compound M6 based on triarylamine:

[0165] Compounds M5-1, M3-2, sodium tert-butoxide, Sphos, and Pd2dba3 were weighed in a molar ratio of 1:1:2:0.02:0.01 and placed in a three-necked flask. 200 ml of anhydrous toluene was added, and the mixture was purged with nitrogen for 15 min. The reaction was then carried out at 130 °C for 8 hours under nitrogen protection. After the reaction was completed, the mixture was cooled to room temperature, extracted with ethyl acetate, and the organic phase was concentrated and subjected to column chromatography to obtain compound M6-1.

[0166] Compound M6-1 was dissolved in dry dichloromethane (DCM), and the mixture was cooled to -45°C under nitrogen protection. A DCM solution of BBr3 (M6-1 to BBr3 in a molar ratio of 1:12) was added dropwise using a syringe. After the addition was complete, the mixture was reacted at 40°C for 18 hours. After the reaction was complete, the reaction solution was poured into ice water, extracted, dried, and then subjected to ethanol slurrying and column chromatography to obtain M6-2.

[0167] Compound M6-2 was dissolved in tetrahydrofuran, followed by the addition of KOH, KI, and 4-bromo-1-butanol (the molar ratio of M6-2, KOH, KI, and 4-bromo-1-butanol was 1:4:0.12:4.5). The mixture was refluxed at 85°C for 10 h under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled, extracted with ethyl acetate, dried, and then slurried with ethanol to obtain M6-3.

[0168] Compound M6-3 was dissolved in dry dichloromethane (DCM, 40 mL), and triethylamine (mole ratio of M6-3 to triethylamine was 1:2) was added. The mixture was cooled to -5°C under a nitrogen atmosphere, and acryloyl chloride (mole ratio of M6-3 to acryloyl chloride was 2:3) was added dropwise using a syringe. After the addition was complete, the reaction mixture was allowed to react at low temperature for 5 h. After the reaction was complete, the reaction solution was poured into ice water, extracted, dried, and then rapidly purified by a neutral alumina column to obtain compound M6 based on a triarylamine. Elemental analysis: (C 94 H 80 N2O 10 Theoretical values: C, 80.78; H, 5.77; N, 2.00; O, 11.45; Measured values: C, 80.93; H, 5.79; N, 2.05; HR-MS (ESI-[M+1]) + (m / z): Theoretical value: 1396.58; Measured value: 1398.59.

[0169] The reaction equation for preparing compound M6 based on triarylamine is as follows:

[0170]

[0171] Example 7

[0172]

[0173] Preparation of compound M7 based on triarylamine:

[0174] Compound M6-2 from Example 6 was dissolved in tetrahydrofuran, and the mixture was cooled to -45°C under nitrogen protection. A tetrahydrofuran solution of 3-bromopropyne (molar ratio of M6-2 to 3-bromopropyne 1:12) and KOH (molar ratio of M6-2 to 3-bromopropyne 1:12) were added dropwise using a syringe. After the addition was complete, the mixture was reacted at 40°C for 18 hours. After the reaction was complete, the reaction solution was poured into ice water, extracted, dried, and then subjected to ethanol slurrying and column chromatography to obtain M7-1.

[0175] The above-mentioned M7-1 (22.6 g, 20 mmol) was dissolved in a mixed solution of tetrahydrofuran and purified water. (4-azido-1-butyl) acrylate (molar ratio of M7-1 to (4-azido-1-butyl) acrylate was added (1:4.5) and copper sulfate (mass ratio of M7-1 to copper sulfate 1:0.02). Ascorbic acid (mass ratio of M7-1 to ascorbic acid 1:0.05) was added in four portions, and the mixture was stirred at room temperature for 6 hours. Extraction with dichloromethane was performed, and after drying, the solution was concentrated to remove some of the solvent. Hexane was added, and a solid precipitated. The solid was collected by filtration and then crystallized from dichloromethane:hexane (1:5 / volume ratio) to obtain the triarylamine-based compound -M7; elemental analysis: (C 100 H 83 N 11 O 10 Theoretical values: C, 75.12; H, 5.23; N, 9.64; O, 10.01; Measured values: C, 75.23; H, 5.29; N, 9.65; HR-MS (ESI-[M+1]) + (m / z): Theoretical value: 1597.63; Measured value: 1599.83.

[0176] The reaction equation for preparing compound M7 based on triarylamines is as follows:

[0177]

[0178] Example 8

[0179] This embodiment provides a structure as shown in formula M8:

[0180]

[0181] Preparation of compound M8 based on triarylamine:

[0182] Compounds M8-1 and M8-2 were weighed in a 1:1 molar ratio and placed in a three-necked flask. 300 mL of anhydrous tetrahydrofuran (THF) was added, and the mixture was cooled to -10 °C under nitrogen protection. NaH was added in portions as the nitrogen flow decreased, resulting in the appearance of a large amount of gas. The mixture was maintained at room temperature for 4 hours until the reaction was complete. The reaction was quenched by adding water, resulting in the precipitation of a large amount of grayish-white solid. The grayish-white solid was filtered and collected. The collected filter cake was dissolved in dichloromethane, filtered through a silica gel pad, and the solid fraction was collected. The solid was recrystallized from toluene to obtain M8-3.

[0183] The above compound M8-3 was dissolved in dry dichloromethane (DCM), and the mixture was cooled to -45°C under nitrogen protection. A DCM solution of BBr3 (M8-3 to BBr3 in a molar ratio of 1:16) was added dropwise using a syringe. After the addition was complete, the mixture was reacted at 40°C for 18 hours. After the reaction was complete, the reaction solution was poured into ice water, extracted, dried, and then subjected to ethanol slurrying and column chromatography to obtain M8-4.

[0184] The above compound M8-4 was dissolved in tetrahydrofuran, followed by the addition of KOH, KI, and 4-bromo-1-butanol (the molar ratio of M8-4, KOH, KI, and 4-bromo-1-butanol was 1:4:0.12:6). The mixture was refluxed at 85°C for 10 h under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled, extracted with ethyl acetate, dried, and then slurried with ethanol to obtain M8-5.

[0185] Compound M8-5 was dissolved in dry dichloromethane (DCM, 40 mL), and triethylamine (mole ratio of M8-5 to triethylamine was 1:8) was added. The mixture was cooled to -5 °C under a nitrogen atmosphere, and acryloyl chloride (mole ratio of M8-5 to acryloyl chloride was 1:2) was added dropwise using a syringe. After the addition was complete, the reaction mixture was allowed to react at low temperature for 5 h. After the reaction was complete, the reaction solution was poured into ice water, extracted, dried, and then rapidly purified by a neutral alumina column to obtain compound M8, which is based on a triarylamine. Elemental analysis: (C 101 H 90 N2O 13 Theoretical values: C, 78.78; H, 5.89; N, 1.82; O, 13.51; Measured values: C, 78.85; H, 5.93; N, 1.87; HR-MS (ESI-[M+1]) + (m / z): Theoretical value: 1538.64; Measured value: 1538.81.

[0186] The reaction equation for preparing compound M8, which is based on triarylamines, is as follows:

[0187]

[0188] Comparative Example

[0189] Comparative Example 1

[0190]

[0191] Preparation of triarylamine compound A1:

[0192] Under nitrogen protection, A1-1, B1-1, palladium acetate, tri-tert-butylphosphine, and sodium tert-butoxide were added to a reaction flask in a molar ratio of 1:1:0.008:0.016:1.2, and 500 ml of toluene was added. The mixture was stirred under reflux for 5 hours, then cooled to room temperature, and water was added. The mixture was then extracted with Z ester of acetate. The organic phase was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the mixture was recrystallized from toluene / ethanol to obtain A1-2.

[0193] Under nitrogen protection, A1-2, B1-2, sodium tert-butoxide, tris(dibenzylacetone)dipalladium, and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (X-phos) were added to a reaction flask in a molar ratio of 1:1:1.2:0.01:0.02, along with 280 ml of toluene. The reaction was carried out under reflux for 7 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and water was added. The organic phase was extracted and separated, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The product was recrystallized from toluene to give compound A1. Elemental analysis: (C 56 H 40 Theoretical values ​​for N: C, 92.53; H, 5.55; N, 1.93; Measured values: C, 92.57; H, 5.61; N, 1.82; HR-MS (ESI-[M+1]) + (m / z): Theoretical value: 726.32; Measured value: 727.45.

[0194] The reaction equation for A1 is:

[0195]

[0196] Comparative Example 2

[0197]

[0198] Preparation of triarylamine compound-A2:

[0199] Compound A2-1, compound A2-2, sodium tert-butoxide, 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (Sphos), and Pd2dba3 were weighed in a molar ratio of 1:1:2:0.02:0.01 and placed in a three-necked flask. 200 ml of anhydrous toluene was added, and the mixture was purged with nitrogen for 15 min. The reaction was then carried out at 120 °C for 8 h under a nitrogen atmosphere. After the reaction was completed, the mixture was cooled to room temperature, extracted with ethyl acetate, and the organic phase was concentrated and subjected to column chromatography to obtain compound A2-3.

[0200] Compound A2-3 was dissolved in dry dichloromethane (DCM), and the solution was cooled to -45°C under a nitrogen atmosphere. A solution of BBr3 (in a molar ratio of 1:4) in dichloromethane (DCM) was added dropwise using a syringe. After the addition was complete, the reaction mixture was allowed to react at 40°C for 18 hours. After the reaction was complete, the reaction solution was poured into ice water, extracted, dried, and then subjected to ethanol slurrying and column chromatography to obtain A2-4.

[0201] Compound A2-4 was dissolved in dry dichloromethane (DCM, 40 mL), and triethylamine (molar ratio of A2-4 to triethylamine 1:2) was added. The mixture was cooled to -5°C under a nitrogen atmosphere, and acryloyl chloride (molar ratio of A2-4 to acryloyl chloride 8:5) was added dropwise using a syringe. After the addition was complete, the reaction mixture was allowed to react at low temperature for 5 hours. After the reaction was complete, the reaction solution was poured into ice water, extracted, dried, and then rapidly purified by a neutral alumina column to obtain the triarylamine compound A2. Elemental analysis: (C 63 H 46 Theoretical N₂O₂ values: C, 87.67; H, 5.37; N, 3.25; O, 3.71; Measured values: C, 87.81; H, 5.42; N, 3.28; HR-MS (ESI-[M+1]) + (m / z): Theoretical value: 862.36, measured value: 863.51.

[0202] The reaction equation for preparing compound A2 based on triarylamine is as follows:

[0203]

[0204] II. Testing Methods

[0205] 1) Testing of HOMO level, LUMO level and Eg

[0206] The HOMO and LUMO energy levels were determined using cyclic voltammetry on an electrochemical workstation (CV Shanghai Chenhua CHI-600E). Platinum wire (Pt) was used as the counter electrode, and silver / silver chloride (Ag / AgCl) was used as the reference electrode. The test was conducted at a scan rate of 100 mV / s in a dichloromethane electrolyte containing 0.1 M tetrabutylammonium hexafluorophosphate under a nitrogen atmosphere. The potential was calibrated using ferrocene. Eg = LUMO - HOMO.

[0207] 2) UV testing

[0208] The absorption spectra of triarylamine-based compounds were tested using a Fuli UV-1900 microscope.

[0209] 3) FL testing

[0210] Fluorescence spectra (phosphorescence spectra) of triarylamine-based compounds were tested using a Hitachi-F-4600 microscope.

[0211] 4) Refractive index testing

[0212] The refractive index of triarylamine-based compounds was tested according to GB / T 6488-2008 standard. The refractive index of the triarylamine-based compounds was measured using an Abbemat 300 refractometer at 20°C.

[0213] 5) Viscosity test

[0214] The viscosity of triarylamine-based compounds was tested in accordance with the GB / T 10247-2008 standard.

[0215] The viscosity of the freshly prepared triarylamine-based compound was tested at 25°C using a slab viscometer, model DVNXRNCP, with an accuracy of ±5 cps.

[0216] 6) Solubility test

[0217] At 25℃, 5g and 10g of the test substance were placed in 10mL of different solvents and stirred to dissolve. If 10g of the test substance was completely dissolved, the solubility of the test substance was judged as "good". If 10g of the test substance could not be completely dissolved, but 5g of the test substance could be completely dissolved, the solubility of the test substance was judged as "medium". If 5g of the test substance could not be completely dissolved, the solubility of the test substance was judged as "poor".

[0218] 7) Testing the transmittance of optical films

[0219] Preparation of the optical film: A triarylamine-based compound, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, photoinitiator TPO, and solvent were mixed in a mass ratio of 36:4.5:4.5:1:49.5 and stirred for 1 hour at a stirring speed of 500 rpm to prepare a transparent adhesive solution. A 4-inch diameter glass slide was placed on a Laurell spin coater, and 2 ml of the above adhesive solution was dropped onto the glass slide using a pipette to prepare a coating. The spin coater was set at a speed of 3000 rpm for 30 seconds. The glass slide was then baked on an 80°C hot plate for 1 minute and cured under a 365 nm UV-LED at a curing energy of 5000 mJ to prepare the optical film.

[0220] The transmittance of the optical film was tested according to GB 2410-2008 standard. The transmittance of the optical film prepared on the glass substrate was tested in the range of 400nm to 800nm ​​using a UV-vis photometer. The testing equipment was a Shimadzu UV-1800.

[0221] Table 1 Performance parameters of each embodiment and comparative example

[0222]

[0223] Table 2. Solubility of triarylamine-based compounds in each example and comparative example.

[0224]

[0225] According to the data in the table above, the triarylamine-based compounds in Examples 1 to 8 have a wide bandgap, their films have weak light absorption in the visible light region, exhibiting excellent visible light transparency, good thermal stability and light stability. More importantly, the triarylamine-based compounds in Examples 1 to 8 have a refractive index higher than 1.85 and excellent solubility in solvents, which is beneficial for preparing high refractive index all-organic photocurable adhesives.

[0226] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this application.

Claims

1. A compound based on triarylamine, characterized in that, The triarylamine-based compounds include compounds with a core structure of bistriarylamine structural units and side chain structures of organic groups containing carbon-carbon double bonds.

2. The triarylamine-based compound according to claim 1, characterized in that, The core structure includes the structure shown in Formula I. Among them, Ar 10 Ar 21 Ar 22 Ar 23 and Ar 24 Each independently includes substituted or unsubstituted C 6～50 aryl, substituted or unsubstituted C 2～50 At least one of the heteroarylene groups. Indicates the binding site; The side chain structure includes at least one of the structures shown in Formula II-1, Formula II-2, Formula II-3, and Formula II-4. Among them, R 21 R 22 R 23 and R 24 Each independently includes substituted or unsubstituted C 1～20 alkoxy, substituted or unsubstituted C 6～20 At least one of the heteroaryl groups; a1, a2, a3 and a4 are each independently 0 or integers from 1 to 12, and a1, a2, a3 and a4 are not all 0 at the same time; X1, X2, X3, and X4 each independently include at least one of hydrogen, vinyl, α-methylvinyl, acryloyl, α-methacryloyl, vinylphenyl, and α-methylvinylphenyl, and X1, X2, X3, and X4 are not all hydrogen. Indicates the binding site.

3. The triarylamine-based compound according to claim 1, characterized in that, The triarylamine-based compounds include compounds with the structure shown in Formula III. Among them, Ar 10 Ar 21 Ar 22 Ar 23 and Ar 24 Each independently includes substituted or unsubstituted C 6～50 aryl, substituted or unsubstituted C 2～50 At least one of the heteroarylene groups; R 21 R 22 R 23 and R 24 Each independently includes substituted or unsubstituted C 1～20 alkoxy, substituted or unsubstituted C 6～20 At least one of the heteroaryl groups; a1, a2, a3, and a4 are each independently 0 or integers from 1 to 12, and a1, a2, a3, and a4 are not all 0 at the same time; X1, X2, X3 and X4 each independently include at least one of hydrogen, vinyl, α-methylvinyl, acryloyl, α-methacryloyl, vinylphenyl, α-methylvinylphenyl, and not all of X1, X2, X3 and X4 are hydrogen at the same time.

4. The triarylamine-based compound according to claim 2, characterized in that, Ar 10 Ar 21 Ar 22 Ar 23 and Ar 24 Each independently comprises at least one of the following: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazole, substituted or unsubstituted thiophene, substituted or unsubstituted thiazolyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted oxadiazinyl, phthalimide, substituted or unsubstituted benzothiophene, substituted or unsubstituted benzofuranyl, substituted or unsubstituted naphtho-(benzofuranyl), substituted or unsubstituted naphthofuranyl, substituted or unsubstituted indolocarbazole, substituted or unsubstituted triphenylene, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, and substituted or unsubstituted quinazolinyl; and / or Ar 10 Ar 21 Ar 22 Ar 23 and Ar 24 Each of these can be independently represented by the following formulas and their derivatives: Among them, Z1, Z2, Z3 and Z4 each independently include hydrogen, deuterium, F, Cl, CN and C. 1～24 Alkyl, C 1～24 At least one of alkoxy, phenyl, biphenyl, naphthyl, triphenylene, anthracene, pyrene, and phenanthrene, wherein d1 and d2 are each independently 0 or integers from 1 to 3. Indicates the binding site; and / or Ar 10 Ar 21 Ar 22 Ar 23 and Ar 24 Each of these can be independently represented by the following formulas and their derivatives: in, Indicates the connection site; T1 and T2 each independently include C 1～24 At least one of the following: alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted phenoxazine group, or substituted or unsubstituted phenothiazine group.

5. The triarylamine-based compound according to any one of claims 1 to 4, characterized in that, The sidechain structure includes At least one of them, The binding sites are represented by m and n, which are independent integers from 1 to 24.

6. The triarylamine-based compound according to any one of claims 1 to 4, characterized in that, X1, X2, X3, and X4 each independently include at least one of hydrogen, vinyl, α-methylvinyl, acryloyl, α-methacryloyl, vinylphenyl, and α-methylvinylphenyl, and at least two of X1, X2, X3, and X4 are not simultaneously hydrogen; or X1, X2, X3, and X4 each independently include at least one of hydrogen, vinyl, α-methylvinyl, acryloyl, α-methacryloyl, vinylphenyl, and α-methylvinylphenyl, and at least three of X1, X2, X3, and X4 are not simultaneously hydrogen; or X1, X2, X3 and X4 each independently include at least one of vinyl, α-methylvinyl, acryloyl, α-methacryloyl, vinylphenyl, and α-methylvinylphenyl.

7. A method for preparing a triarylamine-based compound according to any one of claims 1 to 6, characterized in that, Includes the following steps: Under reactivity conditions, a first raw material comprising a first reactant and a second reactant undergoes a first reaction to prepare a first intermediate; Under reactive conditions, the first intermediate is subjected to a hydroxylation reaction to prepare the second intermediate; Under reactive conditions, the second intermediate is first subjected to a chain extension reaction, followed by an alkenylation reaction, to prepare the triarylamine-based compound; The first reactant includes a compound with the structure shown in Formula IV. Ar 22 and Ar 23 Each independently includes substituted or unsubstituted C 6～50 aryl, substituted or unsubstituted C 2～50 At least one of the heteroarylene groups, Y2 and Y3 each independently include at least one of hydrogen and methoxy groups, and Y2 and Y3 are not both hydrogen; The first reactant includes at least one of the compounds with the structure shown in Formula V and the compounds with the structure shown in Formula VI. Ar 20 Ar 30 Ar 21 and Ar 24 Each independently includes substituted or unsubstituted C 6～50 aryl, substituted or unsubstituted C 2～50 At least one of the heteroarylene groups, Y1 and Y4 each independently include at least one of hydrogen and methoxy groups, and Y5 and Y6 each independently include at least one of F, Br, and Cl.

8. The preparation method according to claim 7, characterized in that, Under reactivity conditions, the chain extension reaction includes: Under reactivity conditions, the second intermediate is reacted with a compound having the structure shown in Formula VIII. Y 10 -R 10 -OH of formula VII R 10 Including substituted or unsubstituted C 1-10 At least one of the alkylene groups, Y 10 Including at least one of bromine, fluorine, and chlorine; and / or The alkenylation reaction includes: Under reactivity conditions, the product of the chain extension reaction is reacted with a third reactant containing a double bond in the second reaction to prepare the triarylamine-based compound; wherein the third reactant containing a double bond includes a compound with the structure shown in Formula VII. R 41 Including at least one of substituted or unsubstituted acyl chloride groups, substituted or unsubstituted benzoic acid groups; and / or The hydroxylating agent for the hydroxylation reaction includes at least one of boron tribromide, boron trichloride, aluminum trichloride, or pyridine hydrochloride; and / or The hydroxylation solvent for the hydroxylation reaction includes at least one of dichloromethane, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, cyclohexane, n-hexane, or petroleum ether.

9. A light-curing adhesive, characterized in that, This includes the triarylamine-based compound according to any one of claims 1 to 6, or the triarylamine-based compound prepared by the preparation method according to claim 7 or 8.

10. The application of the photocurable adhesive of claim 9 in photoresist, lens coating, diffractive waveguide or nanoimprint.

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