Acrylate monomer with high refractive index as well as preparation method and application thereof

Abstract

The invention provides an acrylate monomer with a high refractive index and a preparation method and application thereof, the acrylate monomer has a structure as shown in a formula G1, G2 or G3, the refractive index of the acrylate monomer is 1.75 or above, so that a holographic recording medium has higher sensitivity and higher diffraction efficiency, and the holographic recording medium can be applied to the field of holographic recording. The holographic recording medium is used for a holographic grating, so that the holographic grating has high diffraction efficiency and high refractive index modulation degree.

Description

Technical Field

[0001] The present application belongs to the technical field of optical functional materials, and relates to an acrylate monomer, a preparation method and application thereof, and in particular to a high-refractive-index acrylate monomer, a preparation method and application thereof. Background Art

[0002] The photopolymer materials used for holographic recording primarily consist of components such as photosensitizers, initiators, chain transfer agents, recording monomers, film-forming resins, and plasticizers. Holographic recording is achieved by irradiating the monomers to polymerize, forming a phase-type holographic grating with a modulated refractive index. Monomers in the coherent bright regions are consumed and their concentration decreases, while monomers in the coherent dark regions barely react. This difference in monomer concentration between the bright and dark regions causes monomers in the dark regions to migrate toward the bright regions, while the film-forming resin in the bright regions is squeezed into the dark regions. Ultimately, the refractive index of the bright regions approaches that of the polymer, while the refractive index of the dark regions approaches that of the film-forming resin, thus forming a phase-type volume holographic grating with a modulated refractive index.

[0003] Improving the performance of photopolymers generally requires a lower refractive index for the base resin and a higher refractive index for the writing monomer. However, the refractive index of the writing monomer currently available for photopolymers is typically below 1.6, resulting in a small refractive index difference between the writing monomer and the film-forming resin (usually 0.1-0.2). Increasing the refractive index difference between the writing monomer and the film-forming resin can help achieve higher performance for the photopolymer.

[0004] Therefore, in this field, it is expected to develop acrylic monomers with higher refractive index to increase the refractive index difference between the recording monomer and the film-forming resin, so that the holographic recording medium has higher sensitivity and higher diffraction efficiency, and the holographic grating has better performance. Summary of the Invention

[0005] In view of the deficiencies in the prior art, the purpose of the present application is to provide an acrylate monomer, a preparation method and application thereof, and in particular, to provide a high-refractive-index acrylate monomer, a preparation method and application thereof. The acrylate monomer of the present application has a refractive index of above 1.75, which increases the refractive index difference between the recording monomer and the film-forming resin, so that the holographic recording medium has a higher sensitivity and the recording grating has a higher diffraction efficiency. The holographic recording medium is used to prepare a holographic grating, so that the holographic grating has high diffraction efficiency and high refractive index modulation.

[0006] To achieve this goal, this application adopts the following technical solutions:

[0007] In one aspect, the present application provides an acrylate monomer having a structure shown in Formula G1, G2 or G3:

[0008]

[0009] wherein R1 represents a methyl group or hydrogen, and R2 represents a C1 to C10 straight chain or branched chain alkyl group.

[0010] In the present application, the C1 to C10 straight chain or branched chain alkyl group can be a C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10 straight chain or branched chain alkyl group.

[0011] R2 is selected from the group consisting of a methyl group, an ethyl group, a n-propyl group, an iso-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-decyl group, and the like, wherein the wavy line represents a bonding site of the group.

[0012] On the other hand, the present application provides a method for producing the acrylate monomer as described above, the method comprising the steps of:

[0013] (1) reacting a compound P1 with a compound P2 to obtain a compound P3;

[0014] The compound P1 is any one of the following compounds:

[0015]

[0016] R3 represents Cl, Br or I, and preferably R3 represents Br;

[0017] The compound P2 is the following compound:

[0018] (2) reacting the compound P3 with acryloyl chloride or methacryloyl chloride to obtain an acrylate monomer having a structure represented by Formula G1, G2 or G3.

[0019] The molar ratio of the compound P1 to the compound P2 in step (1) is 1:2 to 4, for example, 1:2, 1:2.3, 1:2.5, 1:2.8, 1:3, 1:3.2, 1:3.5, 1:3.8 or 1:4, and the like.

[0020] The reaction in step (1) is performed in the presence of a catalyst.

[0021] ​In the present application, the catalyst is a commonly used catalyst in the art, including but not limited to Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium), PdCl2(dppf) (bis(diphenylphosphinoferrocene)palladium dichloride), Pd(OAc)2 (palladium acetate), Pd2(dba)3 (tris(dibenzylideneacetone)dipalladium), PdCl2(PPh3)2 (bis(triphenylphosphine)palladium dichloride), Pd(dtbpf)Cl2 (palladium chloride containing di-tert-butylphosphinoferrocene ligand), Pd(PPh3)2Cl2 (bis(triphenylphosphine)palladium dichloride), NiCl2(dppf) (bis(diphenylphosphinoferrocene)nickel chloride), Pd / C (palladium on carbon), Bedford palladium catalyst, DHBOP monodentate phosphine ligand catalysts such as BI-DIME / AntPhos, Pd(tBu)3-G4 (palladium catalyst containing tert-butyl ligand), and Buchwald precatalyst. One or a combination of at least two.

[0022] The amount of the catalyst is 0.5-5 mol% of compound P1, for example, 0.5 mol%, 0.8 mol%, 1 mol%, 1.5 mol%, 1.8 mol%, 2 mol%, 2.5 mol%, 3 mol%, 3.5 mol%, 4 mol%, 4.5 mol% or 5 mol%.

[0023] The reaction in step (1) is carried out in the presence of a ligand.

[0024] In the present application, the ligand is a commonly used ligand in the art, including but not limited to one or a combination of at least two of triphenylphosphine, 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, tricyclohexylphosphine or 1,1'-bis(diphenylphosphino)ferrocene.

[0025] The amount of the ligand used is 1-10 mol% of compound P1, for example, 1 mol%, 1.5 mol%, 2 mol%, 2.5 mol%, 3 mol%, 3.5 mol%, 4 mol%, 4.5 mol%, 5 mol%, 5.5 mol%, 6 mol%, 6.5 mol%, 7 mol%, 7.5 mol%, 8 mol%, 8.5 mol%, 9 mol%, 9.5 mol% or 10 mol%.

[0026] The reaction in step (1) is carried out in the presence of a base.

[0027] In the present application, the base is a commonly used base in the art, including but not limited to potassium carbonate (K2CO2), sodium carbonate (Na2CO3), cesium carbonate (Cs2CO2), potassium phosphate (K2PO4), potassium fluoride (KF), cesium fluoride (CsF), tetrabutylammonium fluoride (TBAF), barium hydroxide (Ba(OH)2), sodium hydroxide (NaOH) or potassium trimethylsilanol (TMSOK) One or a combination of at least two.

[0028] The amount of the base used is 1-3 times the molar amount of compound P1, for example, 1 time, 1.5 times, 1.8 times, 2 times, 2.5 times, 2.8 times or 3 times.

[0029] The reaction in step (1) is carried out in a solvent. The solvent is a commonly used solvent in the art, including but not limited to toluene, dimethoxyethane, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, acetonitrile, dioxane, and a mixed system of water and the above organic solvents (such as toluene / ethanol / water, acetonitrile / water, dioxane / water, etc.), or a combination of at least two of them.

[0030] The reaction temperature of step (1) is 60-120°C, for example 60°C, 70°C, 80°C, 90°C, 100°C, 110°C or 120°C, and the reaction time is 2-24 hours, for example 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 22 hours or 24 hours.

[0031] In this application, the structure of the obtained compound P3 is as follows:

[0032]

[0033] The molar ratio of the hydroxyl group contained in the compound P3 in step (2) to acryloyl chloride or methacryloyl chloride is 1:(1-3), for example, 1:1, 1:1.5, 1:1.8, 1:2, 1:2.3, 1:2.5, 1:2.8 or 1:3.

[0034] In step (2), the acryloyl chloride or methacryloyl chloride is added dropwise to the reaction system containing compound P3.

[0035] The dropwise addition was performed at 0°C.

[0036] The reaction in step (2) is carried out in the presence of an alkaline substance, wherein the alkaline substance includes but is not limited to diisopropylethylamine, pyridine, N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, cesium carbonate, triethylamine, 4-dimethylaminopyridine, triethylenediamine, potassium tert-butoxide, sodium methoxide or sodium ethoxide, or a combination of at least two thereof.

[0037] The molar ratio of the hydroxyl group to the basic substance in the compound P3 is 1:(1-4), for example, 1:1, 1:1.5, 1:1.8, 1:2, 1:2.5, 1:2.8, 1:3, 1:3.3, 1:3.5, 1:3.8 or 1:4.

[0038] The reaction in step (2) is carried out in an ice bath for 0.5 to 10 h, for example, 0.5 h, 0.8 h, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h or 10 h.

[0039] The reaction in step (2) is carried out in a solvent, which includes but is not limited to one or a combination of at least two of ethanol, petroleum ether, dichloromethane, chloroform, ethyl acetate, tetrahydrofuran, acetonitrile, N,N-dimethylformamide or dimethyl sulfoxide; wherein the solvent is any one or a combination of at least two of dichloromethane, chloroform or ethyl acetate.

[0040] In another aspect, the present application provides a photopolymer holographic recording medium, wherein the photopolymer holographic recording medium comprises the following components:

[0041] Component a) a compound having two or more functional groups reactive with isocyanate groups;

[0042] Component b) a polyisocyanate-based compound;

[0043] Component c) an acrylic acid ester monomer as described above;

[0044] Component d) other polymerizable monomers;

[0045] Component e) photosensitive initiation system;

[0046] Component f) chain transfer agent;

[0047] Component g) optional catalyst;

[0048] Component h) optional additives.

[0049] In the present application, it should be noted that the photopolymer holographic recording medium material generally comprises a base resin with a low refractive index and a writing monomer with a high refractive index. In the present application, components a) and b) can form the base resin, while components c) and d) are equivalent to the writing monomer.

[0050] The functional group in component a) that is reactive with an isocyanate group is a hydroxyl group.

[0051] In the present application, component a) is preferably a compound with a low refractive index and two or more hydroxyl groups; preferably any one or a combination of at least two of tetraethylene glycol, trimethylolethane, glycerol, triethanolamine, polyester polyol with a molecular weight of 200 to 2000, polycarbonate polyol with a molecular weight of 200 to 2000 or polyether polyol with a molecular weight of 200 to 2000.

[0052] Based on the total weight of the photopolymer holographic recording medium as 100%, the content of component a) is 8 to 40%, for example, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 33%, 35%, 38% or 40%.

[0053] In the present application, the polyisocyanate compound is preferably a compound with a low refractive index and two or more isocyanate groups; more preferably, it is any one of hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, (2,4,6-trioxotriazine-1,3,5(2H,4H,6H)-triyl)tris(hexamethylene)isocyanate, butane-1,4-diisocyanate, isophorone diisocyanate or dicyclohexylmethane diisocyanate, or a combination of at least two thereof.

[0054] Based on the total weight of the photopolymer holographic recording medium as 100%, the content of component b) is 15-40%, for example, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 33%, 35%, 38% or 40%.

[0055] Based on the total weight of the photopolymer holographic recording medium as 100%, the content of component c) is 0.1 to 30%, for example, 0.1%, 0.5%, 0.8%, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28% or 30%.

[0056] The other polymerizable monomers are selected from at least one of alkenyl naphthalene compounds, alkenyl anthracene compounds, alkenyl benzene compounds, acrylic compounds, methacrylic compounds, acrylate compounds, methacrylate compounds, N-vinyl pyrrole, N-vinyl carbazole, N-vinylimidazole, N-vinyl indole, N-vinyl pyrrolidone or trans-N-3-ynyl butenyl carbazole.

[0057] Illustratively, the alkenylbenzene compound can be selected from at least one of styrene, 2-chlorostyrene, 2-bromostyrene, 3-chlorostyrene, 3-bromostyrene, 4-chlorostyrene, 4-bromostyrene, p-(chloromethyl)styrene or p-(bromomethyl)styrene.

[0058] Exemplarily, the methacrylic acid compound may be methacrylic acid and its derivatives; exemplarily, the acrylate compound may be selected from at least one of pentabromophenyl acrylate, pentachlorophenyl acrylate, phenoxyethyl acrylate, pentabromobenzyl acrylate, 2-naphthyl acrylate, 1,4-di(2-thionaphthyl)2-butyl acrylate, phenoxyethoxyethyl acrylate, bisphenol A diacrylate, tetrabromobisphenol A diacrylate, 2-phenoxyethyl acrylate, benzyl acrylate, p-chlorophenyl acrylate, 2,4,6-trichlorophenyl acrylate, p-bromophenyl acrylate, 2,4,6-tribromophenyl acrylate, propane-2,2-diylbis[(2,6-dibromo-4,1-phenylene)oxy(2-{[3,3,3-tris(4-chlorophenyl)propionyl]oxy}propane-3,1-diyl)oxyethane-2,1-diyl] diacrylate, etc.

[0059] Illustratively, the methacrylate compound can be selected from at least one of 2-phenoxyethyl methacrylate, benzyl methacrylate, p-bromophenyl methacrylate, p-chlorophenyl methacrylate, 2,4,6-trichlorophenyl methacrylate, pentabromophenyl methacrylate, pentachlorophenyl methacrylate, phenoxyethyl methacrylate, phenoxyethoxyethyl methacrylate, 1,4-di(2-thionaphthyl)2-butyl methacrylate, pentabromobenzyl methacrylate, 2-naphthyl methacrylate, bisphenol A dimethacrylate, tetrabromobisphenol A dimethacrylate, and the like.

[0060] For example, the vinylanthracene compound may be selected from 2-vinylanthracene, 9-vinylanthracene, and the like.

[0061] For example, the vinyl naphthalene compound can be selected from 1-vinyl naphthalene, 2-vinyl naphthalene, and the like.

[0062] Based on the total weight of the photopolymer holographic recording medium as 100%, the content of component d) is 10 to 40%, for example, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 33%, 35%, 38% or 40%.

[0063] In the present application, the photopolymer holographic recording medium further comprises component e) a photosensitive initiating system.

[0064] The photosensitive initiation system includes a photoinitiator and an optional photosensitizer, and more preferably a combination of a photoinitiator and a photosensitizer.

[0065] The mass ratio of the photosensitizer to the photoinitiator is 0.001-1:0.1-3, for example, 0.001:0.1, 0.001:0.5, 0.001:0.8, 0.001:1, 0.001:1.5, 0.001:1.8, 0.001:2, 0.001:2.5, 0.001:2.8, 0.001:3, 0.01:0.1, 0.01:0.5, 0.01:0.8, 0.01:1, 0.01:1.5, 0.01:1.8, 0.01:2, 0.01:2.5, 0.01:2.8, 0.01:3, 0.1:0.1, 0.1:0.5, 0.1:0.8 , 0.1:1, 0.1:1.5, 0.1:1.8, 0.1:2, 0.1:2.5, 0.1:2.8, 0.1:3, 0.5:0.1, 0.5:0.8, 0.5:1, 0.5:1.5, 0.5:1.8, 0.5:2, 0.5:2.5, 0.5:2.8, 0.5:3, 0.8:0.1, 0.8:0.5, 0.8:1, 0.8:1.5, 0.8:1.8, 0.8:2, 0.8:2.5, 0.8:2.8, 0.8:3, 1:0.1, 1:0.5, 1:0.8, 1:1.5, 1:1.8, 1:2, 1:2.5, 1:2.8 or 1:3.

[0066] In the present application, different broadband responses can be achieved by adjusting the type of photosensitizer. However, when a photoinitiator with an adapted wavelength is selected in the raw material of the photopolymer holographic recording medium of the present application, the photosensitizer may not be added.

[0067] Exemplarily, the photosensitizer is a dye having a high electron transfer efficiency under illumination, including but not limited to any one or a combination of at least two of cyanine dyes, fluorescein dyes, coumarin ketone dyes, nitrogen-containing aromatic heterocyclic compounds, aromatic amine compounds, or benzylcycloalkane ketone compounds. For example, it includes one or a combination of at least two of new methylene blue, thionine, basic yellow, pinacol chloride, rhodamine 6G, gallocyanine, ethyl violet, Victoria Blue R, lapis lazuli blue, methylene blue, Astrazon Orange G, Darrow Red, Pyrrole Red Y, Basic Red 29, Quinaldine Red, Crystal Violet, Ethyl Violet, Brilliant Green, pyri11lium I, Azure A, Crystal Violet White Nitrile, or Malachite Green White Nitrile.

[0068] Furthermore, the photoinitiator is an initiator that can be activated by actinic radiation and initiate polymerization of the corresponding polymerizable groups, including but not limited to aromatic ketone compounds, benzoin and its derivatives, benzil ketal, acylphosphine oxide, aryl ammonium borate, chromium salts, aryl diazonium salts, onium salts, organometallic compounds, or mixtures of these compounds in any proportion. For example, the present invention includes one or a combination of at least two of benzophenone, alkylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, anthrone and halogenated benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bisacylphosphine oxide, phenyl glyoxylate, camphorquinone, α-aminoalkyl phenone, α,α-dialkoxyacetophenone, α-hydroxyalkyl phenone, tetrabutylammonium triphenylhexylborate, tetrabutylammonium tris-(3-fluorophenyl)hexylborate, tetrabutylammonium tris-(3-chloro-4-methylphenyl)hexylborate, ferrocenyl compounds, iodonium salts, sulfonium salts or hexaarylbisimidazoles.

[0069] Based on 100% of the total weight of the photopolymer holographic recording medium, the content of component e) is 0.1-3%, for example, 0.1%, 0.5%, 0.8%, 1%, 1.5%, 1.8%, 2%, 2.5%, 2.8% or 3%.

[0070] In the present application, the photopolymer holographic recording medium further includes component f) a chain transfer agent.

[0071] The chain transfer agent is a thiol compound, including but not limited to one or a combination of at least two of dodecyl mercaptan, mercaptoethanol, hexanethiol, phenylethyl mercaptan, 5-(4-pyridyl)-1,3,4-oxadiazole-2-thiol or 4-methyl-4H-1,2,4-triazole-3-thiol.

[0072] Based on 100% of the total weight of the photopolymer holographic recording medium, the content of component f) is 0.1-3%, for example, 0.1%, 0.5%, 0.8%, 1%, 1.5%, 1.8%, 2%, 2.5%, 2.8% or 3%.

[0073] In the present application, the optional catalyst of component g) is included, which means that the catalyst may be contained or not. The photopolymer type holographic recording medium preferably includes the catalyst of component g).

[0074] The catalyst is selected from at least one of a tertiary amine catalyst or an organometallic catalyst, including but not limited to triethylenediamine, bis(dimethylaminoethyl) ether, dimethylethanolamine, 2-(2-dimethylamino-ethoxy)ethanol, trimethylhydroxyethylpropylenediamine, N,N-bis(dimethylaminopropyl)isopropanolamine, dibutyltin dilaurate, stannous octoate, potassium carboxylate catalyst or bismuth carboxylate catalyst, or a combination of at least two thereof.

[0075] Based on the total weight of the photopolymer holographic recording medium as 100%, the content of component g) is 0.1 to 5%, for example, 0.1%, 0.5%, 0.8%, 1%, 1.5%, 1.8%, 2%, 2.5%, 2.8%, 3%, 3.5%, 4%, 4.5% or 5%.

[0076] In the present application, the optional additives of component h) are included, which means that the additives may be present or not. The photopolymer holographic recording medium preferably includes the additives of component h).

[0077] The additive is selected from one or a combination of at least two of a defoamer, a leveling agent, a plasticizer or a water remover.

[0078] Based on the total weight of the photopolymer holographic recording medium as 100%, the content of component h) is 0.1 to 10%, for example, 0.1%, 0.5%, 0.8%, 1%, 1.5%, 1.8%, 2%, 2.5%, 2.8%, 3%, 3.5%, 4%, 4.5%, 5%, 6%, 7%, 8%, 9% or 10%.

[0079] When the additive includes a defoaming agent, the content of the defoaming agent is no more than 3% based on 100% of the total weight of the photopolymer holographic recording medium.

[0080] Furthermore, when the additives include a leveling agent, the content of the leveling agent is no more than 3% based on 100% of the total weight of the photopolymer holographic recording medium.

[0081] Further, when the plasticizer is included in the additive, the content of the plasticizer is not more than 3% based on the total weight of the photopolymer type holographic recording medium.

[0082] The defoaming agent is a silicone defoaming agent, such as BYK-011, BYK-012, BYK-014, BYK-023, BYK-051N, BYK-085, BYK-1610, BYK-1707, BYK-1740, BYK-1760 produced by BYK, DC65, AFE-7820 produced by Dow Corning, or any proportion mixture of these defoaming agents.

[0083] The leveling agent is a silicone surface agent, such as BYK-302, BYK-306, BYK-307, BYK-327, BYK-329, BYK-333, BYK-356, BYK-358, BYK-378, BYK-3455, BYK-3566 produced by BYK, or any proportion mixture of these surface agents.

[0084] The plasticizer is toluene, xylene, dimethylformamide, dimethylacetamide, glycerol, phthalate, or any proportion mixture of these compounds.

[0085] The water removing agent includes but is not limited to p-methylbenzenesulfonyl isocyanate, triethyl orthoformate, CUWR-WB20 water removing agent produced by Guangzhou Yourun Synthetic Material Co., Ltd., ALT-201 water removing agent produced by Anxiang Ailite Chemical Co., Ltd., PCCI water removing agent produced by Shanghai Lur Chemical Industry Trade Co., Ltd., etc.

[0086] In another aspect, the present application provides a holographic grating, and the raw material for preparing the holographic grating includes the photopolymer type holographic recording medium as described above.

[0087] In another aspect, the present application provides a holographic optical element, and the raw material for preparing the holographic optical element includes the photopolymer type holographic recording medium as described above.

[0088] In another aspect, the present application provides an optical display device, and the optical display device includes the photopolymer type holographic recording medium as described above or the holographic optical element as described above.

[0089] Compared with the prior art, the present application has the following beneficial effects:

[0090] This application provides a high-refractive-index acrylate monomer with a refractive index of 1.75 or greater. Using it in the production of photopolymer holographic recording media can effectively increase the refractive index difference between the recording monomer and the film-forming resin, resulting in a holographic recording medium with multiple excellent properties, including high sensitivity, high diffraction efficiency, and high refractive index modulation. Its diffraction efficiency is greater than 95%, its sensitivity is greater than 100 cm / mJ, and its exposure dose is less than 20 mJ / cm 2 , and use it in holographic gratings, so that the holographic gratings can have high diffraction efficiency and high refractive index modulation. BRIEF DESCRIPTION OF THE DRAWINGS

[0091] Figure 1 These are diffraction efficiency diagrams of the photopolymer holographic recording media prepared in Examples 7-9 at different exposure doses.

[0092] Figure 2 These are diffraction efficiency diagrams of the photopolymer holographic recording media prepared in Examples 10-12 at different exposure doses.

[0093] Figure 3 This is a diffraction efficiency diagram of the photopolymer holographic recording medium prepared in Comparative Example 1 under different exposure doses. DETAILED DESCRIPTION

[0094] The technical solution of the present application is further described below through specific implementation methods. Those skilled in the art should understand that the embodiments are only used to help understand the present application and should not be regarded as specific limitations of the present application.

[0095] Example 1

[0096] Preparation of compound M-1:

[0097]

[0098] The preparation method specifically comprises the following steps:

[0099] S1: Dissolve 1 equivalent of compound 1, catalyst tetrakis(triphenylphosphine)palladium (2 mol% of compound 1), ligand triphenylphosphine (5 mol% of compound 1), sodium carbonate (twice the molar amount of compound 1), and 2 equivalents of compound 2 in toluene solvent, heat to 80°C, and react for 8 hours with stirring. After the reaction, remove excess solvent by rotary evaporation, and separate by column chromatography to obtain the target product 3.

[0100] S2: Compound 3 and triethylamine (the molar ratio of hydroxyl group and triethylamine in compound 3 is 1:1) are dissolved in an organic solvent, dichloromethane, under ice bath. After stirring for 10 minutes, acryloyl chloride (the molar ratio of hydroxyl group and acryloyl chloride in compound 3 is 1:1) is added dropwise to the mixed solution of compound 3 and triethylamine at 0°C. After reacting for 0.5 hours under ice bath, dilute hydrochloric acid is added dropwise to remove excess acryloyl chloride. The mixture is washed with saturated NaCl solution, saturated NaHCO3 solution and deionized water in sequence. The organic phase is dried over anhydrous sodium sulfate, and the excess solvent is removed by rotary evaporation. The target monomer M-1 is separated by column chromatography.

[0101] 1 H NMR (600MHz, CDCl3) δ8.24–8.20(m,1H),7.67–7.63(m,1H),7.59–7.53(m,2H),7.31–7.25(m,2H),6. 15–6.04(m,1H),5.95–5.89(m,1H),5.89–5.82(m,1H),4.32(t,J=7.5Hz,2H),3.25(t,J=7.6Hz,2H).

[0102] 13 C NMR (151MHz, CDCl3) δ166.43,166.40,142.75,142.72,142.45,142.42,136.17,136.11,135.03,135.01,133.81,131.92,131.91,128.41,128.3 9,128.13,128.11,128.10,128.08,128.05,121.46,121.44,121.41,121 .38,118.00,117.98,117.95,66.28,66.26,66.25,66.23,33.74,33.72.

[0103] Example 2

[0104] Synthesis of compound M-2

[0105]

[0106] The preparation method specifically comprises the following steps:

[0107] Compound 3 and triethylamine (the molar ratio of hydroxyl group and triethylamine in compound 3 is 1:2) are dissolved in an organic solvent, dichloromethane, under an ice bath. After stirring for 10 minutes, methacryloyl chloride (the molar ratio of hydroxyl group and methacryloyl chloride in compound 3 is 1:2) is added dropwise to the mixed solution of compound 3 and triethylamine at 0°C. After reacting for 0.5 hours under an ice bath, dilute hydrochloric acid is added dropwise to remove excess methacryloyl chloride. The mixture is washed with saturated NaCl solution, saturated NaHCO3 solution and deionized water in sequence. The organic phase is dried over anhydrous sodium sulfate, and the excess solvent is removed by rotary evaporation. The target monomer M-2 is separated by column chromatography.

[0108] 1 H NMR (600MHz, CDCl3) δ8.24–8.20(m,1H),7.67–7.63(m,1H),7.60–7.54(m,2H),7.31–7.25(m,2H),5.75(dq,J=1 .9, 0.9Hz, 1H), 5.62 (dq, J = 1.7, 0.9Hz, 1H), 4.31 (t, J = 7.5Hz, 2H), 3.28 (t, J = 7.5Hz, 2H), 1.94 (t, J = 0.8Hz, 3H).

[0109] 13 C NMR (151MHz, CDCl3) δ167.65,167.62,142.75,142.72,142.47,142.45,142.42,136.4 1,136.40,136.35,136.34,136.06,134.82,134.80,134.78,133.70,128.31,128.30,1 28.00,127.98,127.97,127.95,127.92,126.15,126.11,121.42,121.40,121.37,121.35,117.45,117.43,117.40,66.62,66.60,66.59,66.57,33.32,33.30,18.29,18.25.

[0110] Example 3

[0111] Synthesis of compound M-3

[0112]

[0113] The preparation method comprises the following steps:

[0114] S1: 1 equivalent of compound 6, catalyst tetrakis(triphenylphosphine)palladium (1 mol% of compound 6), ligand triphenylphosphine (1 mol% of compound 6), potassium carbonate (equimolar amount of compound 6), 2 equivalents of compound 2 were dissolved in solvent toluene, heated to 100°C, stirred for 4 hours, after the reaction was completed, the excess solvent was removed by rotary evaporation, column chromatography was used to separate to obtain the target product 7.

[0115] S2: Compound 7 and triethylamine (molar ratio of hydroxyl in compound 7 to triethylamine 1:3) were dissolved in organic solvent dichloromethane under ice bath, after stirring for 10 min, acryloyl chloride (molar ratio of hydroxyl in compound 7 to acryloyl chloride 1:1) was added dropwise to the mixed solution of compound 7 and triethylamine at 0°C, after reaction for 0.5 h under ice bath, dilute hydrochloric acid was added dropwise to remove excess acryloyl chloride, saturated NaCl solution, saturated NaHCO3 solution and deionized water were used in sequence, the organic phase was dried over anhydrous sodium sulfate, the excess solvent was removed by rotary evaporation, column chromatography was used to separate to obtain the target monomer M-3.

[0116] 1 H NMR (600 MHz, CDC13) δ 7.80 (s, 1H), 7.49-7.43 (m, 2H), 7.34-7.28 (m, 2H), 6.15-6.04 (m, 1H), 5.88 (ddd, J = 15.7, 3.1, 1.5 Hz, 2H), 4.32 (t, J = 7.5 Hz, 2H), 4.02 (t, J = 8.4 Hz, 2H), 3.25 (t, J = 7.6 Hz, 2H), 1.68 (dddd, J = 17.2, 9.1, 8.3, 0.9 Hz, 2H), 1.56-1.45 (m, 2H), 0.97 (t, J = 5.6 Hz, 3H).

[0117] 13C NMR (151MHz, CDCl3) δ166.43,166.39,144.27,144.23,139.76,139.73,136.46,134.93,133.90, 131.82,131.81,128.41,128.39,128.21,128.19,128.00,127.98,127.95,127.92,125.10,117. 43,117.40,117.37,117.35,72.05,72.03,72.01,71.99,66.43,66.41,66.40,66.38,33.21,33.19,31.68,31.66,31.64,31.62,19.22,19.20,19.19,19.17,19.14,13.80,13.78,13.76,13.74.

[0118] Example 4

[0119] Synthesis of compound M-4

[0120]

[0121] The preparation method comprises the following steps:

[0122] S1: Dissolve 1 equivalent of compound 8, catalyst tetrakis(triphenylphosphine)palladium (5 mol% of compound 8), ligand triphenylphosphine (3 mol% of compound 8), potassium carbonate (3 times the molar amount of compound 8), and 2 equivalents of compound 2 in tetrahydrofuran solvent, heat to 60°C, and react with stirring for 24 hours. After the reaction, remove excess solvent by rotary evaporation, and separate by column chromatography to obtain the target product 9.

[0123] S2: Compound 9 and triethylamine (the molar ratio of hydroxyl group and triethylamine in compound 9 is 1:2) are dissolved in an organic solvent, dichloromethane, under ice bath. After stirring for 10 minutes, methacryloyl chloride (the molar ratio of hydroxyl group and methacryloyl chloride in compound 9 is 1:2) is added dropwise to the mixed solution of compound 9 and triethylamine at 0°C. After reacting for 0.5 hours under ice bath, dilute hydrochloric acid is added dropwise to remove excess methacryloyl chloride. The mixture is washed with saturated NaCl solution, saturated NaHCO3 solution and deionized water in sequence. The organic phase is dried over anhydrous sodium sulfate, and the excess solvent is removed by rotary evaporation. The target monomer M-4 is separated by column chromatography.

[0124] 1H NMR (600 MHz, CDC13) δ 7.80 (s, 1H), 7.46 - 7.40 (m, 2H), 7.33 - 7.27 (m, 2H), 5.75 (dq, J = 1.9, 0.9 Hz, 1H), 5.62 (dq, J = 1.8, 0.9 Hz, 1H), 4.31 (t, J = 7.5 Hz, 2H), 4.00 (t, J = 8.0 Hz, 2H), 3.27 (t, J = 7.5 Hz, 2H), 1.93 (t, J = 0.9 Hz, 3H), 1.87 - 1.77 (m, 2H), 1.47 (pd, J = 8.5, 0.7 Hz, 2H), 1.41 - 1.24 (m, 6H), 0.93 - 0.85 (m, 3H).

[0125] 13 C NMR (151 MHz, CDC13) δ 167.59, 143.92, 138.87, 136.98, 135.44, 135.31, 128.63, 127.86, 127.37, 126.76, 124.90, 122.91, 70.35, 67.49, 37.29, 31.90, 30.52, 29.09, 26.83, 22.94, 17.92, 14.38.

[0126] Example 5

[0127] Synthesis of compound M-5

[0128]

[0129]

[0130] The preparation method comprises the following steps:

[0131] S1: dissolve 1 equivalent of compound 10, catalyst tetrakis(triphenylphosphine)palladium (used in an amount of 3 mol% of compound 10), ligand triphenylphosphine (used in an amount of 1 mol% of compound 10), potassium carbonate (used in an amount of equimolar amount of compound 10), and 2 equivalents of compound 2 in solvent toluene, heat to 80°C, stir for 12 hours, after the reaction is completed, remove the excess solvent by rotary evaporation, and separate the target product 11 by column chromatography.

[0132] S2: Compound 11 and triethylamine (the molar ratio of hydroxyl group and triethylamine in compound 11 is 1:2) are dissolved in an organic solvent, dichloromethane, under ice bath. After stirring for 10 minutes, acryloyl chloride (the molar ratio of hydroxyl group and acryloyl chloride in compound 11 is 1:2) is added dropwise to the mixed solution of compound 11 and triethylamine at 0°C. After reacting for 0.5 hours under ice bath, dilute hydrochloric acid is added dropwise to remove excess acryloyl chloride. The mixture is washed with saturated NaCl solution, saturated NaHCO3 solution and deionized water in sequence. The organic phase is dried over anhydrous sodium sulfate, and the excess solvent is removed by rotary evaporation. The target monomer M-5 is separated by column chromatography.

[0133] 1 H NMR (600MHz, CDCl3) δ7.84(s,1H),7.59–7.53(m,2H),7.33–7.27(m,2H),7.25(d,J=6.6Hz,1H),6.88(d,J=6.6Hz,1H),6.15–6.04(m,1H),5.88(dd d,J=15.7,3.1,1.5Hz,2H),4.32(t,J=7.5Hz,2H),3.24(t,J=7.6Hz,2H), 2.70(t,J=7.8Hz,2H), 1.67(tq,J=7.9,5.3Hz,2H), 0.99(t,J=5.2Hz,3H).

[0134] 13 C NMR (151MHz, CDCl3) δ166.88,144.32,139.38,137.20,136.31,135.44,134.15,132.01,129.48,127 .89(d,J=6.2Hz),127.42(d,J=13.8Hz),127.03,126.87,124.22,67.78,37.29,35.88,23.12,14.23.

[0135] Example 6

[0136] Synthesis of compound M-6

[0137]

[0138] S1: Dissolve 1 equivalent of compound 12, catalyst tris(dibenzylideneacetone)dipalladium (1 mol% of compound 12), ligand 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (1 mol% of compound 12), potassium carbonate (equimolar to compound 12), and 2 equivalents of compound 2 in toluene solvent, heat to 100°C, and react with stirring for 10 hours. After the reaction, remove excess solvent by rotary evaporation, and separate by column chromatography to obtain the target product 13.

[0139] S2: Compound 13 and triethylamine (the molar ratio of hydroxyl group and triethylamine in compound 13 is 1:4) are dissolved in an organic solvent under ice bath. After stirring for 10 minutes, acryloyl chloride (the molar ratio of hydroxyl group and acryloyl chloride in compound 13 is 1:1) is added dropwise to the mixed solution of compound 13 and triethylamine at 0°C. After reacting for 0.5 hours under ice bath, dilute hydrochloric acid is added dropwise to remove excess acryloyl chloride. The mixture is washed with saturated NaCl solution, saturated NaHCO3 solution and deionized water in sequence. The organic phase is dried over anhydrous sodium sulfate, and the excess solvent is removed by rotary evaporation. The target monomer M-6 is separated by column chromatography.

[0140] 1 H NMR(600MHz, CDCl3)δ7.79(s,1H),7.59–7.53(m,2H),7.32–7.26(m,2H),7.25(d,J=7 .1Hz,1H),6.90(d,J=7.0Hz,1H),6.13–6.05(m,1H),5.91(dd,J=12.2,2.5Hz,1H),5. 86(dd,J=12.0,2.5Hz,1H),4.37–4.26(m,2H),3.24(t,J=7.6Hz,2H),2.77(d,J=11.2 Hz,2H),1.96–1.84(m,1H),1.44–1.35(m,3H),1.35–1.26(m,5H),0.95–0.86(m,6H).

[0141] 13 C NMR (151MHz, CDCl3) δ 166.88, 144.32, 137.62, 136.31, 135.87, 135.23, 133.45, 132.01, 129.90 (d, J = 11.4Hz), 129. 35,128.45,127.91,127.49,127.01,121.60,67.49,39.15,37.07,36.77,29.82,29.28,27.26,23.44,14.36,12.03.

[0142] Example 7

[0143] This embodiment provides a photopolymer holographic recording medium, the raw material components of which are shown in Table 1:

[0144] Table 1

[0145]

[0146]

[0147] Example 8

[0148] This embodiment provides a photopolymer holographic recording medium, the raw material components of which are shown in Table 2:

[0149] Table 2

[0150]

[0151] Example 9

[0152] This embodiment provides a photopolymer holographic recording medium, the raw material components of which are shown in Table 3:

[0153] Table 3

[0154]

[0155]

[0156] Example 10

[0157] This embodiment provides a photopolymer holographic recording medium, the raw material components of which are shown in Table 4:

[0158] Table 4

[0159]

[0160] Example 11

[0161] This embodiment provides a photopolymer holographic recording medium, the raw material components of which are shown in Table 5:

[0162] Table 5

[0163]

[0164] Example 12

[0165] This embodiment provides a photopolymer holographic recording medium, the raw material components of which are shown in Table 6:

[0166] Table 6

[0167]

[0168]

[0169] Comparative Example 1

[0170] The only difference from Example 7 is that component c is not contained.

[0171] Test example

[0172] The refractive index of the monomers synthesized in Examples 1 to 6 was measured using an Abbe refractometer. The specific monomer refractive indexes are shown in Table 7 below:

[0173] Table 7

[0174] monomer M-1 M-2 M-3 M-4 M-5 M-6 Refractive index 1.76 1.75 1.78 1.76 1.79 1.78

[0175] The performance of the photopolymer holographic recording media containing high-refractive-index monomers of Examples 7 to 12 and the conventional photopolymer holographic recording medium of the comparative example were tested. During the test, the holographic recording media in the Examples were exposed to lasers of different wavelengths (532 nm for Example 7, 633 nm for Example 8, 633 nm for Example 9, 457 nm for Example 10, 532 nm for Example 11, and 457 nm for Example 12) depending on the photosensitive system. The exposure intensity was 3 mW / cm 2 .

[0176] Specifically, for the above holographic recording medium, a solid-state laser with the wavelength mentioned above was selected as the light source. After passing through a beam expander, a beam splitter, and a half-wave plate, two beams with the same light intensity and a diameter of 8 mm were obtained. The two beams intersected in the prepared holographic recording medium for exposure, and the light intensity was 3 mW / cm 2 The detection light source is a 785nm wavelength solid-state laser that does not react with the recording medium. The detection light is incident on the exposure area from the Bragg angle. The transmitted light and diffracted light are monitored in real time by a photodetector. The single grating diffraction efficiency (η) and the photosensitivity (S) of the photopolymer holographic recording medium are calculated using formulas (1) to (3).

[0177]

[0178] Where η is the diffraction efficiency, η max is the highest diffraction efficiency, I d is the diffracted light intensity, in mW / cm 2 ;I t is the transmitted light intensity, in mW / cm 2 ; S is photosensitivity; E is exposure energy, unit is mJ; d E represents the derivative of E; d represents the thickness of the sample, in cm; ΔE is the exposure energy when the highest diffraction efficiency is achieved, in mJ.

[0179] The holographic performance test results of the photopolymer holographic recording medium in the embodiment and the ordinary photopolymer holographic recording medium in the comparative example are as follows: Figure 1-Figure 3 shown.

[0180] Table 8 records the performance data obtained from the test.

[0181] Table 8

[0182]

[0183]

[0184] As can be seen from Table 8, the acrylic ester monomers of the present application can make the diffraction efficiency of the photopolymer holographic recording medium greater than 95%, the sensitivity greater than 100 cm / mJ, and the exposure less than 20 mJ / cm 2 , which can make the holographic grating have high diffraction efficiency and high refractive index modulation.

[0185] The applicant declares that while the above-mentioned examples are used to illustrate the acrylate monomers, their preparation methods, and applications, this application is not limited to these examples. This does not imply that this application must rely on these examples for implementation. Persons skilled in the art should understand that any improvements to this application, equivalent replacements for raw materials in the products of this application, addition of auxiliary ingredients, and selection of specific methods, etc., fall within the scope of protection and disclosure of this application.

Claims

1. An acrylic acid ester monomer, characterized in that: The acrylic acid ester monomer has a structure shown in Formula G1, G2 or G3: Wherein, R1 represents a methyl group or hydrogen, and R2 represents a C1-C10 straight-chain or branched alkyl group.

2. The acrylic acid ester monomer according to claim 1, wherein R2 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl or n-decyl, where the wavy line represents the point of attachment of the group.

3. The method for preparing an acrylic acid ester monomer according to claim 1 or 2, wherein: The preparation method comprises the following steps: (1) Compound P1 reacts with compound P2 to obtain compound P3; Compound P1 is any one of the following compounds: R3 represents Cl, Br or I, preferably R3 represents Br; Compound P2 is the following compound: (2) Compound P3 reacts with acryloyl chloride or methacryloyl chloride to obtain an acrylate monomer having a structure represented by formula G1, G2 or G3.

4. The preparation method according to claim 3, characterized in that The molar ratio of compound P1 to compound P2 in step (1) is 1:2-4; The reaction in step (1) is carried out in the presence of a catalyst, wherein the catalyst is one or a combination of at least two of tetrakis(triphenylphosphine)palladium, bis(diphenylphosphinoferrocene)palladium dichloride, palladium acetate, tris(dibenzylideneacetone)dipalladium, bis(triphenylphosphine)palladium dichloride, palladium chloride containing a di-tert-butylphosphinoferrocene ligand, bis(diphenylphosphinoferrocene)nickel chloride, Pd / C, Bedford palladium catalyst, DHBOP monodentate phosphine ligand catalyst, palladium catalyst containing a tert-butyl ligand, or Buchwald precatalyst; The amount of the catalyst is 0.5-5 mol% of compound P1; The reaction in step (1) is carried out in the presence of a ligand, wherein the ligand is one or a combination of at least two of triphenylphosphine, 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, tricyclohexylphosphine or 1,1'-bis(diphenylphosphino)ferrocene; The amount of the ligand is 1-10 mol% of compound P1; The reaction in step (1) is carried out in the presence of a base, wherein the base is selected from one or a combination of at least two of potassium carbonate, sodium carbonate, cesium carbonate, potassium phosphate, potassium fluoride, cesium fluoride, tetrabutylammonium fluoride, barium hydroxide, sodium hydroxide or potassium trimethylsilanol; The amount of the base used is 1-3 times the molar amount of compound P1; The reaction in step (1) is carried out in a solvent selected from one or a combination of at least two of toluene, dimethoxyethane, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, acetonitrile, dioxane, and a mixed system of water and the above-mentioned organic solvents; The reaction temperature in step (1) is 60-120° C., and the reaction time is 2-24 hours.

5. The preparation method according to claim 3, characterized in that The molar ratio of the hydroxyl group contained in the compound P3 in step (2) to acryloyl chloride or methacryloyl chloride is 1:(1-3); Step (2) adding the acryloyl chloride or methacryloyl chloride dropwise to the reaction system containing compound P3 at 0°C; The reaction in step (2) is carried out in the presence of an alkaline substance, wherein the alkaline substance includes any one or a combination of at least two of diisopropylethylamine, pyridine, N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, cesium carbonate, triethylamine, 4-dimethylaminopyridine, triethylenediamine, potassium tert-butoxide, sodium methoxide or sodium ethoxide; The molar ratio of the hydroxyl group to the alkaline substance in the compound P3 is 1:(1-4); The reaction in step (2) is carried out in an ice bath for 0.5 to 10 h; The reaction in step (2) is carried out in a solvent, which includes one or a combination of at least two of ethanol, petroleum ether, dichloromethane, chloroform, ethyl acetate, tetrahydrofuran, acetonitrile, N,N-dimethylformamide or dimethyl sulfoxide; wherein the solvent is any one or a combination of at least two of dichloromethane, chloroform or ethyl acetate.

6. A photopolymer holographic recording medium, characterized in that: The photopolymer holographic recording medium comprises the following components: Component a) a compound having two or more functional groups reactive with isocyanate groups; Component b) a polyisocyanate-based compound; Component c) the acrylic acid ester monomer according to claim 1 or 2; Component d) other polymerizable monomers; Component e) photosensitive initiation system; Component f) chain transfer agent; Component g) optional catalyst; Component h) optional additives.

7. The photopolymer holographic recording medium according to claim 6, wherein: The functional group capable of reacting with an isocyanate group in component a) is a hydroxyl group; Component a) is any one or a combination of at least two of tetraethylene glycol, trimethylolethane, glycerol, triethanolamine, polyester polyol with a molecular weight of 200-2000, polycarbonate polyol with a molecular weight of 200-2000, or polyether polyol with a molecular weight of 200-2000; Based on 100% of the total weight of the photopolymer holographic recording medium, the content of the component a) is 8 to 40%.

8. The photopolymer holographic recording medium according to claim 6, wherein: The polyisocyanate compound is any one of hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, (2,4,6-trioxotriazine-1,3,5(2H,4H,6H)-triyl)tris(hexamethylene)isocyanate, butane-1,4-diisocyanate, isophorone diisocyanate or dicyclohexylmethane diisocyanate, or a combination of at least two thereof; Based on 100% of the total weight of the photopolymer holographic recording medium, the content of the component b) is 15 to 40%.

9. The photopolymer holographic recording medium according to claim 6, wherein: Based on 100% of the total weight of the photopolymer holographic recording medium, the content of the component c) is 1 to 30%.

10. The photopolymer holographic recording medium according to claim 6, wherein The other polymerizable monomers are selected from at least one of alkenyl naphthalene compounds, alkenyl anthracene compounds, alkenyl benzene compounds, acrylic compounds, methacrylic compounds, acrylate compounds, methacrylate compounds, N-vinyl pyrrole, N-vinyl carbazole, N-vinylimidazole, N-vinyl indole, N-vinyl pyrrolidone or trans-N-3-ynyl butenyl carbazole; Based on 100% by weight of the total weight of the photopolymer holographic recording medium, the content of the component d) is 10 to 40%.

11. The photopolymer holographic recording medium according to claim 6, wherein The photosensitive initiation system includes a combination of a photoinitiator and a photosensitizer, wherein the mass ratio of the photosensitizer to the photoinitiator is 0.001-1:0.1-3; The content of the component e) is 0.1 to 3% based on the total weight of the photopolymer holographic recording medium as 100%; The chain transfer agent is a mercaptan compound including one or a combination of at least two of dodecyl mercaptan, mercaptoethanol, hexanethiol, phenylethyl mercaptan, 5-(4-pyridyl)-1,3,4-oxadiazole-2-thiol or 4-methyl-4H-1,2,4-triazole-3-thiol; The content of the component f) is 0.1 to 3% based on the total weight of the photopolymer holographic recording medium as 100%; The catalyst is selected from at least one of a tertiary amine catalyst or an organometallic catalyst; The content of component g) is 0.1 to 5% based on the total weight of the photopolymer holographic recording medium as 100%; The additive is selected from one or a combination of at least two of a defoamer, a leveling agent, a plasticizer or a water remover; Based on 100% by weight of the total weight of the photopolymer holographic recording medium, the content of the component h) is 0.1 to 10%.

12. A holographic grating, characterized in that: The raw material for preparing the holographic grating includes the photopolymer holographic recording medium according to any one of claims 6 to 11.

13. A holographic optical element, characterized in that: The raw material for preparing the holographic optical element comprises the photopolymer holographic recording medium according to any one of claims 6 to 11.

14. An optical display device, characterized in that: The optical display device comprises the photopolymer holographic recording medium according to any one of claims 6 to 11, the holographic grating according to claim 12, or the holographic optical element according to claim 13.

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