Polymerizable monomer with refractive index greater than 1.7 and preparation method and application thereof

Abstract

The invention provides a polymerizable monomer with the refractive index larger than 1.7 and a preparation method and application thereof.The polymerizable monomer has the structure shown in the formula G1 or G2 or G3 or G4 or G5 or G6, the refractive index of the polymerizable monomer is 1.7 or above, and therefore a holographic recording medium has various excellent characteristics such as high sensitivity, high diffraction efficiency and high refractive index modulation degree; 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 a polymerizable monomer, a preparation method and application thereof, and in particular to a polymerizable monomer with a refractive index greater than 1.7, 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 polymerizable 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, so as to obtain a holographic grating with high diffraction efficiency and high refractive index modulation. Summary of the Invention

[0005] In response to the shortcomings of the prior art, the present application aims to provide a polymerizable monomer, a preparation method, and applications thereof, and in particular, to a polymerizable monomer having a refractive index greater than 1.7, a preparation method, and applications thereof. The polymerizable monomer of the present application has a refractive index greater than 1.7, which increases the refractive index difference between the recording monomer and the film-forming resin, resulting in a holographic recording medium with higher sensitivity and a recording grating with higher diffraction efficiency. The holographic recording medium can be used to prepare a holographic grating, resulting in a holographic grating with 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 a polymerizable monomer having a structure shown in Formula G1, G2, G3, G4, G5 or G6:

[0008]

[0009] Wherein, R1 represents methyl or hydrogen, R2 represents

[0010] On the other hand, the present application provides a method for preparing the polymerizable monomer as described above, the preparation method comprising the following steps:

[0011] The polymerizable monomers of the structures shown in formula G1, G2, and G3 are prepared by the following steps:

[0012] (1) Compound P1 reacts with compound P2 to obtain compound P3;

[0013] Compound P1 is any one of the following compounds:

[0014]

[0015] Compound P2 is: wherein X1 is selected from Cl, Br or I, preferably Br;

[0016] (2) Compound P3 reacts with acryloyl chloride or methacryloyl chloride to obtain a polymerizable monomer having a structure represented by formula G1, G2, or G3;

[0017] Alternatively, the polymerizable monomers of the structures shown in formula G1, G2, and G3 are prepared by the following steps:

[0018] (A) Compound P4 reacts with Compound P5 to obtain Compound P3;

[0019] Compound P4 is any one of the following compounds:

[0020] Wherein X2 is selected from Cl, Br or I, preferably Br;

[0021] Compound P5 is:

[0022] (B) Compound P3 reacts with acryloyl chloride or methacryloyl chloride to obtain polymerizable monomers having structures represented by formulas G1, G2, and G3.

[0023] The polymerizable monomers of the structures shown in formula G4, G5, and G6 are prepared by the following steps:

[0024] (i) Compound P3 reacts with Compound P6 to obtain polymerizable monomers having structures represented by Formulas G4, G5, and G6;

[0025] Compound P6 is any one of the following compounds:

[0026] Wherein X3 is selected from Cl, Br or I, preferably Br.

[0027] In step (1), the molar ratio of the boronic acid functional group in compound P1 to the bromine functional group in compound P2 is 1 to 2:1, for example, 1:1, 1.2:1, 1.5:1, 1.8:1 or 2:1.

[0028] The reaction in step (1) is carried out in the presence of a catalyst.

[0029] 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.

[0030] 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%.

[0031] The reaction in step (1) is carried out in the presence of a ligand.

[0032] 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.

[0033] 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%.

[0034] The reaction in step (1) is carried out in the presence of a base.

[0035] In the present application, the base is a commonly used base in the art, including but not limited to potassium carbonate (K2CO3), sodium carbonate (Na2CO3), cesium carbonate (Cs2CO3), potassium phosphate (K3PO4), 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] In this application, the structure of the obtained compound P3 is as follows:

[0040]

[0041] 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.

[0042] In step (2), the acryloyl chloride or methacryloyl chloride is added dropwise to the reaction system containing compound P3.

[0043] The dropwise addition was performed at 0°C.

[0044] 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 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.

[0045] 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.

[0046] 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.

[0047] 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; the solvent is any one or a combination of at least two of dichloromethane, chloroform or ethyl acetate.

[0048] In step (A), the molar ratio of the bromine functional group in compound P4 to the boronic acid functional group in compound P5 is 1:1-2, for example, 1:1, 1:1.2, 1:1.5, 1:1.8 or 1:2.

[0049] The reaction in step (A) is carried out in the presence of a catalyst.

[0050] 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.

[0051] The amount of the catalyst is 0.5-5 mol% of compound P4, 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%.

[0052] The reaction in step (A) is carried out in the presence of a ligand.

[0053] 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.

[0054] The amount of the ligand used is 1-10 mol% of compound P4, 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%.

[0055] The reaction in step (A) is carried out in the presence of a base.

[0056] In the present application, the base is a commonly used base in the art, including but not limited to potassium carbonate (K2CO3), sodium carbonate (Na2CO3), cesium carbonate (Cs2CO3), potassium phosphate (K3PO4), 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.

[0057] The amount of the base used is 1-3 times the molar amount of compound P4, for example, 1 time, 1.5 times, 1.8 times, 2 times, 2.5 times, 2.8 times or 3 times.

[0058] The reaction in step (A) 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 mixture 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.

[0059] The reaction temperature of step (A) 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.

[0060] The molar ratio of the hydroxyl group contained in the compound P3 in step (B) 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.

[0061] In step (B), the acryloyl chloride or methacryloyl chloride is added dropwise to the reaction system containing compound P3.

[0062] The dropwise addition was performed at 0°C.

[0063] The reaction in step (B) is carried out in the presence of a basic substance, and the basic substance includes but is not limited to 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.

[0064] 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.

[0065] The reaction in step (B) 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.

[0066] The reaction in step (B) 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; the solvent is any one or a combination of at least two of dichloromethane, chloroform or ethyl acetate.

[0067] In step (i), the molar ratio of the hydroxyl functional group in compound P3 to the bromine functional group in compound P6 is 1:1-2, for example, 1:1, 1:1.2, 1:1.4, 1:1.5, 1:1.8 or 1:2.

[0068] The reaction in step (i) is carried out in the presence of a deprotonating agent.

[0069] The deprotonating agent is any one of n-butyl lithium, tert-butyl lithium, phenyl lithium, sodium hydride, potassium hydride, sodium amide, potassium amide, sodium bis(trimethylsilyl)amide, potassium tert-butoxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, triethylamine, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,8-diazabicyclo[5.4.0]undec-7-ene, or a combination of at least two thereof.

[0070] In the step (i), the molar ratio of the hydroxyl functional group to the deprotonating agent in the compound P3 is 1:1 to 2, for example, 1:1, 1:1.2, 1:1.4, 1:1.5, 1:1.8 or 1:2.

[0071] The deprotonating agent is added dropwise to the reaction system containing compound P3 under ice bath. After the addition is completed, the temperature is returned to room temperature and stirred for 0.5 to 2 h (e.g., 0.5 h, 1 h, 1.5 h, 1.8 h or 2 h). Then, compound P6 is added dropwise under ice bath and stirred for 0.1 to 10 h, e.g., 0.5 h, 1 h, 3 h, 5 h, 8 h or 10 h.

[0072] The reaction in step (i) is carried out in a solvent, and the solvent is selected from one or a combination of at least two of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, ethylene glycol dimethyl ether, 1,4-dioxane, toluene, benzene, diethyl ether, methyl tert-butyl ether, n-hexane or cyclohexane.

[0073] In another aspect, the present application provides a photopolymer holographic recording medium, wherein the photopolymer holographic recording medium comprises the following components:

[0074] Component a) a compound having two or more functional groups reactive with isocyanate groups;

[0075] Component b) a polyisocyanate-based compound;

[0076] Component c) a polymerizable monomer as described above;

[0077] Component d) other polymerizable monomers;

[0078] Component e) photosensitive initiation system;

[0079] Component f) Chain transfer agent.

[0080] 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.

[0081] The functional group in component a) that is reactive with an isocyanate group is a hydroxyl group.

[0082] 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.

[0083] 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%.

[0084] 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.

[0085] 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%.

[0086] 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%.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] For example, the vinylanthracene compound may be selected from 2-vinylanthracene, 9-vinylanthracene, and the like.

[0092] For example, the vinyl naphthalene compound can be selected from 1-vinyl naphthalene, 2-vinyl naphthalene, and the like.

[0093] 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%.

[0094] In the present application, the photopolymer holographic recording medium further comprises component e) a photosensitive initiating system.

[0095] The photosensitive initiation system includes a photoinitiator and an optional photosensitizer, and more preferably a combination of a photoinitiator and a photosensitizer.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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%.

[0101] In the present application, the photopolymer holographic recording medium further includes component f) a chain transfer agent.

[0102] 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.

[0103] 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%.

[0104] The photopolymer holographic recording medium further comprises component g) a catalyst.

[0105] 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.

[0106] 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%.

[0107] The photopolymer holographic recording medium further comprises a component h) an additive.

[0108] 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.

[0109] 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%.

[0110] 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.

[0111] 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.

[0112] Furthermore, when the additive includes a plasticizer, the content of the plasticizer is no more than 3% based on 100% of the total weight of the photopolymer holographic recording medium.

[0113] The defoaming agent is an organosilicon 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 a mixture of these defoaming agents in any proportion.

[0114] The leveling agent is an organosilicon surface additive, 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 a mixture of these surface additives in any proportion.

[0115] The plasticizer is toluene, xylene, dimethylformamide, dimethylacetamide, glycerol, phthalate or a mixture of these compounds in any proportion.

[0116] The dehydrating agent includes but is not limited to p-toluenesulfonyl isocyanate, triethyl orthoformate, CUWR-WB20 dehydrating agent of Guangzhou Yourun Synthetic Materials Co., Ltd., ALT-201 dehydrating agent of Anxiang Elite Chemical Co., Ltd., PCCI dehydrating agent of Shanghai Ruhr Chemical Trading Co., Ltd., etc.

[0117] In another aspect, the present application provides a holographic grating, wherein the raw material for preparing the holographic grating includes the photopolymer holographic recording medium as described above.

[0118] In another aspect, the present application provides a holographic optical element, wherein the raw materials for preparing the holographic optical element include the photopolymer holographic recording medium as described above.

[0119] In another aspect, the present application provides an optical display device, comprising the photopolymer holographic recording medium, the holographic grating, or the holographic optical element as described above.

[0120] Compared with the prior art, this application has the following beneficial effects:

[0121] This application provides a high-refractive-index polymerizable monomer with a refractive index of 1.7 or higher. 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. The diffraction efficiency is greater than 95%, the sensitivity is greater than 100 cm / mJ, and the exposure dose is less than 20 mJ / cm 2 , and use it in holographic gratings, so that the holographic gratings can have high sensitivity, high diffraction efficiency and high refractive index modulation. BRIEF DESCRIPTION OF THE DRAWINGS

[0122] Figure 1 These are diffraction efficiency diagrams of the photopolymer holographic recording media prepared in Examples 10-14 at different exposure doses.

[0123] Figure 2 These are diffraction efficiency diagrams of the photopolymer holographic recording media prepared in Examples 15-18 at different exposure doses.

[0124] 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

[0125] 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.

[0126] Example 1

[0127] Synthesis of compound M-1

[0128]

[0129]

[0130] The preparation method comprises the following steps:

[0131] S1: Dissolve 1 mol of compound 1, 0.02 mol of catalyst tetrakis(triphenylphosphine)palladium, 0.04 mol of ligand triphenylphosphine, 2 mol of sodium carbonate, and 1 mol of compound 2 in 200 mL of solvent toluene, heat to 80°C, and react for 10 hours with stirring. After the reaction is completed, remove the excess solvent by rotary evaporation, and separate by column chromatography to obtain the target product 3.

[0132] S2: Dissolve 1 mol of compound 3 and 1 mol of triethylamine in 200 mL of organic solvent dichloromethane under ice bath. After stirring for 10 min, add 1 mol of acryloyl chloride dropwise to the mixed solution of compound 3 and triethylamine at 0°C. After reacting for 0.5 h under ice bath, add dilute hydrochloric acid dropwise to remove excess acryloyl chloride or methacryloyl chloride. Wash with saturated NaCl solution, saturated NaHCO3 solution and deionized water in sequence. After drying the organic phase over anhydrous sodium sulfate, remove excess solvent by rotary evaporation, and separate by column chromatography to obtain the target monomer M-1.

[0133] 1 H NMR (600MHz, CDCl3) δ7.63–7.56(m,3H),7.41–7.27(m,8H),6.14–6.04(m,1H),5.91(dd,J=1 7.7, 2.7Hz, 1H), 5.85 (dd, J = 17.2, 2.7Hz, 1H), 4.32 (t, J = 7.6Hz, 2H), 3.24 (t, J = 7.6Hz, 2H).

[0134] 13 C NMR (151MHz, CDCl3) δ166.35,138.24,137.16,136.32,136.27,134.83,134.36,134.32,132.08, 128.39,128.32,127.93,127.62,127.38,127.07,127.02,126.93,126.66,126.54,65.78,34.03.

[0135] Example 2

[0136] Synthesis of compound M-2

[0137]

[0138] The preparation method comprises the following steps:

[0139] S1: Dissolve 1 mol of compound 5, 0.01 mol of catalyst tetrakis(triphenylphosphine)palladium, 0.01 mol of ligand triphenylphosphine, 1 mol of potassium carbonate, and 1 mol of compound 2 in 200 mL of solvent toluene, heat to 100°C, and react for 4 hours with stirring. After the reaction is completed, remove the excess solvent by rotary evaporation, and separate by column chromatography to obtain the target product 6.

[0140] S2: 1 mol of compound 6 and 3 mol of triethylamine were dissolved in 200 mL of organic solvent dichloromethane under ice bath. After stirring for 10 min, 1 mol of methacryloyl chloride was added dropwise to the mixed solution of compound 6 and triethylamine at 0°C. After reacting for 0.5 h under ice bath, dilute hydrochloric acid was added dropwise to remove excess methacryloyl chloride. The mixture was washed with saturated NaCl solution, saturated NaHCO3 solution and deionized water in sequence. The organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by rotary evaporation. The target monomer M-2 was obtained by column chromatography.

[0141] 1 H NMR(600MHz, CDCl3)δ7.59(dd,J=7.5,2.2Hz,1H),7.57–7.51(m,3H),7.40(d,J=7.5Hz,1H),7.36–7.26(m,6H),5 .81(p,J=1.5Hz,1H), 5.59(p,J=1.5Hz,1H), 4.32(t,J=7.5Hz,2H), 3.27(t,J=7.5Hz,2H), 1.94(t,J=1.4Hz,3H).

[0142] 13 C NMR (151MHz, CDCl3) δ167.67,136.98,135.93,135.35,134.56,128.41,128.23,127.96, 127.65,127.57,127.51,127.01,126.96,126.90,126.56,126.16,66.41,33.92,18.29.

[0143] Example 3

[0144] Synthesis of compound M-3

[0145]

[0146] The preparation method comprises the following steps:

[0147] S1: Dissolve 1 mol of compound 8, 0.03 mol of catalyst tetrakis(triphenylphosphine)palladium, 0.05 mol of ligand triphenylphosphine, 1 mol of potassium carbonate, and 2 mol of compound 2 in 200 mL of tetrahydrofuran solvent, heat to 70°C, and react with stirring for 24 hours. After the reaction is completed, remove the excess solvent by rotary evaporation, and separate by column chromatography to obtain the target product 9.

[0148] S2: 1 mol of compound 9 and 3 mol of triethylamine were dissolved in 200 mL of organic solvent dichloromethane under ice bath. After stirring for 10 min, 1 mol of acryloyl chloride was added dropwise to the mixed solution of compound 9 and triethylamine at 0°C. After reacting for 0.5 h under ice bath, dilute hydrochloric acid was added dropwise to remove excess acryloyl chloride. The mixture was washed with saturated NaCl solution, saturated NaHCO3 solution and deionized water in sequence. The organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by rotary evaporation. The target monomer M-3 was separated by column chromatography.

[0149] 1 H NMR (600MHz, CDCl3) δ7.59 (dd, J=7.5, 2.2Hz, 1H), 7.57–7.50 (m, 3H), 7.36 (d, J=7.6Hz, 1H), 7.32 –7.26(m,2H),6.15–6.04(m,1H),5.93–5.85(m,2H),4.32(t,J=7.5Hz,2H),3.24(t,J=7.6Hz,2H).

[0150] 13 C NMR (151MHz, CDCl3) δ166.39,138.94,137.29,136.31,135.29,135.03,131.88,128.07,127.81,127.59,126.53,66.26,33.44.

[0151] Example 4

[0152] Synthesis of compound M-4

[0153]

[0154]

[0155] The preparation method comprises the following steps:

[0156] S1: Dissolve 1 mol of compound 10, 0.01 mol of catalyst tetrakis(triphenylphosphine)palladium, 0.02 mol of ligand triphenylphosphine, 1 mol of potassium carbonate, and 1 mol of compound 11 in 200 mL of solvent toluene, heat to 120°C, and react for 4 hours with stirring. After the reaction is completed, remove the excess solvent by rotary evaporation, and separate by column chromatography to obtain the target product 3.

[0157] S2: 1 mol of compound 3 and 2 mol of triethylamine were dissolved in 200 mL of organic solvent dichloromethane under ice bath. After stirring for 10 min, 1 mol of methacryloyl chloride was added dropwise to the mixed solution of compound 3 and triethylamine at 0°C. After reacting for 0.5 h under ice bath, dilute hydrochloric acid was added dropwise to remove excess methacryloyl chloride. The mixture was washed with saturated NaCl solution, saturated NaHCO3 solution and deionized water in sequence. The organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by rotary evaporation. The target monomer M-4 was separated by column chromatography.

[0158] 1 H NMR (600MHz, CDCl3) δ7.62–7.53(m,3H),7.41–7.27(m,9H),5.78(dq,J=1.9,0.9Hz,1H),5.6 3(dq,J=1.8,0.8Hz,1H), 4.32(t,J=7.5Hz,2H), 3.27(t,J=7.5Hz,2H), 1.94(t,J=0.8Hz,3H).

[0159] 13 C NMR (151MHz, CDCl3) δ167.67,138.24,136.23,135.93,134.85,134.63,134.57,128 .96,128.43,127.64,127.40,127.08,126.67,126.49,126.16,66.41,33.92,18.29.

[0160] Example 5

[0161] Synthesis of compound M-5

[0162]

[0163]

[0164] The preparation method comprises the following steps:

[0165] S1: Dissolve 1 mol of compound 12, 0.005 mol of catalyst tetrakis(triphenylphosphine)palladium, 0.1 mol of ligand triphenylphosphine, 1 mol of potassium carbonate, and 1 mol of compound 11 in 200 mL of solvent toluene, heat to 80°C, and react for 10 hours with stirring. After the reaction is completed, remove the excess solvent by rotary evaporation, and separate by column chromatography to obtain the target product 6.

[0166] S2: 1 mol of compound 6 and 3 mol of triethylamine were dissolved in 200 mL of organic solvent dichloromethane under ice bath. After stirring for 10 min, 1 mol of acryloyl chloride was added dropwise to the mixed solution of compound 6 and triethylamine at 0°C. After reacting for 0.5 h under ice bath, dilute hydrochloric acid was added dropwise to remove excess acryloyl chloride. The mixture was washed with saturated NaCl solution, saturated NaHCO3 solution and deionized water in sequence. The organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by rotary evaporation. The target monomer M-5 was separated by column chromatography.

[0167] 1 H NMR(600MHz, CDCl3)δ7.60(dd,J=7.5,2.2Hz,1H),7.57–7.51(m,3H),7.40(d,J=7.6Hz,1H),7.36–7.28(m,6H),6.13– 6.04(m,1H),5.91(dd,J=12.3,2.6Hz,1H),5.85(dd,J=11.9,2.6Hz,1H),4.32(t,J=7.6Hz,2H),3.24(t,J=7.5Hz,2H).

[0168] 13 C NMR (151MHz, CDCl3) δ166.38,138.40,137.07,135.42,135.35,134.27,133.90,132.10, 128.39,128.34,128.13,127.65,127.57,127.49,126.97,126.90,126.54,65.80,34.03.

[0169] Example 6

[0170] Synthesis of compound M-6

[0171]

[0172] The preparation method comprises the following steps:

[0173] S1: Dissolve 1 mol of compound 13, 0.03 mol of catalyst tetrakis(triphenylphosphine)palladium, 0.03 mol of ligand triphenylphosphine, 1 mol of potassium carbonate, and 1 mol of compound 11 in 200 mL of solvent toluene, heat to 90°C, and react for 12 hours with stirring. After the reaction is completed, remove the excess solvent by rotary evaporation, and separate by column chromatography to obtain the target product 9.

[0174] S2: 1 mol of compound 9 and 3 mol of triethylamine were dissolved in 200 mL of organic solvent dichloromethane under ice bath. After stirring for 10 min, 1 mol of methacryloyl chloride was added dropwise to the mixed solution of compound 9 and triethylamine at 0°C. After reacting for 0.5 h under ice bath, dilute hydrochloric acid was added dropwise to remove excess methacryloyl chloride. The mixture was washed with saturated NaCl solution, saturated NaHCO3 solution and deionized water in sequence. The organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by rotary evaporation. The target monomer M-6 was separated by column chromatography.

[0175] 1 H NMR (600MHz, CDCl3) δ7.60–7.51(m,6H),7.52(d,J=2.3Hz,2H),7.37(d,J=7.5Hz,2H),7.32–7.26(m,4H),5.81(p,J=1.5Hz,1H),5. 75(dq,J=1.9,0.9Hz,1H), 5.61(ddt,J=16.1,2.7,1.1Hz,2H), 4.31(t,J=7.5Hz,4H), 3.28(t,J=7.5Hz,4H), 1.93(d,J=1.3Hz,6H).

[0176] 13 C NMR (151MHz, CDCl3) δ167.66,138.91,137.06,136.37,136.06,135.29,135.03,128.81,128.12,127.92,127.60,126.13,66.54,33.30,18.25.

[0177] Example 7

[0178] Synthesis of compound M-7

[0179]

[0180] The preparation method comprises the following steps:

[0181] 1 mol of compound 3 was dissolved in 200 mL of N,N-dimethylformamide, and 1 mol of deprotonating agent sodium carbonate was slowly added under ice bath. After the addition was completed, the temperature was returned to room temperature and stirred for 1 hour. Then, 1 mol of compound 14 was added under ice bath and the stirring reaction was continued for 0.5 hour. After the reaction was completed, the organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by rotary evaporation. Compound M-7 was obtained by column chromatography.

[0182] 1 H NMR (600MHz, CDCl3) δ7.63–7.56(m,3H),7.41–7.34(m,3H),7.37–7.28(m,5H),5.86(tt,J=17.2,6.7Hz,1H),5.24(dd, J=17.0, 2.4Hz, 1H), 5.16 (dd, J= 17.0, 2.4Hz, 1H), 4.07 (d, J= 6.6Hz, 2H), 3.62 (t, J= 7.1Hz, 2H), 3.17 (t, J= 7.1Hz, 2H).

[0183] 13 C NMR (151MHz, CDCl3) δ138.45,137.29,136.33,134.72,133.74,128.19,128 .17,127.75,127.52,127.10,127.04,126.67,117.43,71.92,69.40,34.33.

[0184] Example 8

[0185] Synthesis of compound M-8

[0186]

[0187] The preparation method comprises the following steps:

[0188] 1 mol of compound 6 was dissolved in 200 mL of N,N-dimethylformamide, and 1 mol of deprotonating agent sodium carbonate was slowly added under ice bath. After the addition was completed, the temperature was returned to room temperature and stirred for 2 h. Then, 1 mol of compound 15 was added under ice bath and the stirring reaction was continued for 3 h. After the reaction was completed, the organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by rotary evaporation. Compound M-8 was obtained by column chromatography.

[0189] 1H NMR (600MHz, CDCl3) δ7.63–7.56(m,1H),7.59–7.51(m,1H),7.40(d,J=7.6Hz,0H ),7.36–7.28(m,3H),4.19(s,1H),3.72(t,J=6.4Hz,1H),3.21(t,J=6.4Hz,1H).

[0190] 13 C NMR (151MHz, CDCl3) δ138.09,137.14,134.27,128.49,128.40,128.37,127.77 ,127.69,127.59,127.09,127.02,126.63,79.45,75.31,71.10,59.44,34.46.

[0191] Example 9

[0192] Synthesis of compound M-9

[0193]

[0194] The preparation method comprises the following steps:

[0195] 1 mol of compound 9 was dissolved in 200 mL of N,N-dimethylformamide, and 2 mol of deprotonating agent sodium carbonate was slowly added under ice bath. After the addition was completed, the temperature was returned to room temperature and stirred for 0.5 h. Then, 2 mol of compound 14 was added under ice bath and the stirring reaction was continued for 5 h. After the reaction was completed, the organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by rotary evaporation. Compound M-9 was obtained by column chromatography.

[0196] 1 H NMR(600MHz, CDCl3)δ7.58(dd,J=7.5,2.2Hz,2H),7.57–7.51(m,6H),7.37(d,J=7.5Hz,2H),7.32–7.26(m,4H),5.93–5.80(m,2H), 5.24(dd,J=17.2,2.3Hz,1H),5.22(s,1H),5.20–5.13(m,2H),4.07(d,J=6.7Hz,4H),3.62(t,J=7.0Hz,4H),3.18(t,J=7.1Hz,4H).

[0197] 13C NMR (151MHz, CDCl3) δ139.05,137.46,136.22,135.37,135.05,133.43,128.66,127.80,127.59,126.55,71.96,69.66,34.19.

[0198] Example 10

[0199] This embodiment provides a photopolymer holographic recording medium, the raw material components of which are shown in Table 1:

[0200] Table 1

[0201]

[0202] Example 11

[0203] This embodiment provides a photopolymer holographic recording medium, the raw material components of which are shown in Table 2:

[0204] Table 2

[0205]

[0206] Example 12

[0207] This embodiment provides a photopolymer holographic recording medium, the raw material components of which are shown in Table 3:

[0208] Table 3

[0209]

[0210] Example 13

[0211] This embodiment provides a photopolymer holographic recording medium, the raw material components of which are shown in Table 4:

[0212] Table 4

[0213]

[0214] Example 14

[0215] This embodiment provides a photopolymer holographic recording medium, the raw material components of which are shown in Table 5:

[0216] Table 5

[0217]

[0218] Example 15

[0219] This embodiment provides a photopolymer holographic recording medium, the raw material components of which are shown in Table 6:

[0220] Table 6

[0221]

[0222] Example 16

[0223] This embodiment provides a photopolymer holographic recording medium, the raw material components of which are shown in Table 7:

[0224] Table 7

[0225]

[0226] Example 17

[0227] This embodiment provides a photopolymer holographic recording medium, the raw material components of which are shown in Table 8:

[0228] Table 8

[0229]

[0230] Example 18

[0231] This embodiment provides a photopolymer holographic recording medium, the raw material components of which are shown in Table 9:

[0232] Table 9

[0233]

[0234] Comparative Example 1

[0235] The only difference from Example 10 is that component c is not contained.

[0236] Test example

[0237] The refractive index of the monomers synthesized in Examples 1 to 6 was measured using an Abbe refractometer. The specific refractive index of the monomers is shown in Table 10 below:

[0238] Table 10

[0239] monomer M-1 M-2 M-3 M-4 M-5 M-6 M-7 M-8 M-9 Refractive index 1.73 1.72 1.71 1.72 1.74 1.7 1.74 1.74 1.71

[0240] The performance of the photopolymer holographic recording media containing high-refractive-index monomers of Examples 10 to 18 and the conventional photopolymer holographic recording medium of the comparative example were tested. During the tests, the holographic recording media in the Examples were exposed to lasers of different wavelengths (532 nm for Example 10, 590 nm for Example 11, 457 nm for Example 12, 570 nm for Example 13, 532 nm for Example 14, 457 nm for Example 15, 610 nm for Example 16, 633 nm for Example 17, and 580 nm for Example 18) according to their different photosensitive systems. The exposure intensity was 3 mW / cm2 .

[0241] 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).

[0242]

[0243] 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.

[0244] 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.

[0245] Table 11 records the performance data obtained from the test.

[0246] Table 11

[0247]

[0248] As can be seen from Table 11, the polymerizable 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 amount less than 20 mJ / cm 2 , which can make the holographic grating have high diffraction efficiency and high refractive index modulation.

[0249] The applicant declares that this application uses the above-mentioned embodiments to illustrate the polymerizable monomers, preparation methods, and applications of the present application, but this application is not limited to the above-mentioned embodiments, that is, it does not mean that this application must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvements to this application, equivalent replacements for various raw materials in the products of this application, addition of auxiliary components, and selection of specific methods, etc., are all within the scope of protection and disclosure of this application.

Claims

1. A polymerizable monomer, characterized in that The polymerizable monomer has a structure shown in formula G1, G2, G3, G4, G5 or G6: Wherein, R1 represents methyl or hydrogen, R2 represents 2. The method for preparing a polymerizable monomer according to claim 1, wherein The preparation method comprises the following steps: The polymerizable monomers of the structures shown in formula G1, G2, and G3 are prepared by the following steps: (1) Compound P1 reacts with compound P2 to obtain compound P3; Compound P1 is any one of the following compounds: Compound P2 is: wherein X1 is selected from Cl, Br or I; (2) Compound P3 reacts with acryloyl chloride or methacryloyl chloride to obtain a polymerizable monomer having a structure represented by formula G1, G2, or G3; Alternatively, the polymerizable monomers of the structures shown in formula G1, G2, and G3 are prepared by the following steps: (A) Compound P4 reacts with Compound P5 to obtain Compound P3; Compound P4 is any one of the following compounds: wherein X2 is selected from Cl, Br or I; Compound P5 is: (B) reacting compound P3 with acryloyl chloride or methacryloyl chloride to obtain a polymerizable monomer having a structure represented by formula G1, G2, or G3; The polymerizable monomers of the structures shown in formula G4, G5, and G6 are prepared by the following steps: (i) Compound P3 reacts with Compound P6 to obtain polymerizable monomers having structures represented by Formulas G4, G5, and G6; Compound P6 is any one of the following compounds: wherein X3 is selected from Cl, Br or I.

3. The preparation method according to claim 2, characterized in that In step (1), the molar ratio of the boronic acid functional group in the compound P1 to the bromine functional group in the compound P2 is 1 to 2:1; The reaction in step (1) is carried out in the presence of a catalyst; 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(triphenylphosphine)dichloropalladium, 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; 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; 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.

4. The preparation method according to claim 2, 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); In step (2), the acryloyl chloride or methacryloyl chloride is added dropwise to the reaction system containing compound P3; the addition is carried out at 0°C; The reaction in step (2) is carried out in the presence of an alkaline substance, wherein the alkaline substance is 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; the solvent is any one or a combination of at least two of dichloromethane, chloroform or ethyl acetate.

5. The preparation method according to claim 2, characterized in that In step (A), the molar ratio of the bromine functional group in compound P4 to the boronic acid functional group in compound P5 is 1:1-2; The reaction in step (A) is carried out in the presence of a catalyst; 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(triphenylphosphine)dichloropalladium, 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 P4; The reaction in step (A) is carried out in the presence of a ligand; 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 P4; The reaction in step (A) is carried out in the presence of a base; 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 P4; The reaction in step (A) 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 mixture of water and the above organic solvents; The reaction temperature in step (A) is 60-120° C., and the reaction time is 2-24 hours. The molar ratio of the hydroxyl group contained in the compound P3 in step (B) to acryloyl chloride or methacryloyl chloride is 1:(1-3); In step (B), the acryloyl chloride or methacryloyl chloride is added dropwise to the reaction system containing compound P3; the addition is carried out at 0°C; The reaction in step (B) is carried out in the presence of a basic substance, wherein the basic substance is 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 (B) is carried out in an ice bath for 0.5 to 10 hours; The reaction in step (B) 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; the solvent is any one or a combination of at least two of dichloromethane, chloroform or ethyl acetate.

6. The preparation method according to claim 2, characterized in that In step (i), the molar ratio of the hydroxyl functional group in compound P3 to the bromine functional group in compound P6 is 1:1-2; The reaction in step (i) is carried out in the presence of a deprotonating agent; The deprotonating agent is any one of n-butyllithium, tert-butyllithium, phenyllithium, sodium hydride, potassium hydride, sodium amide, potassium amide, sodium bis(trimethylsilyl)amide, potassium tert-butoxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, triethylamine, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,8-diazabicyclo[5.4.0]undec-7-ene, or a combination of at least two thereof; In the step (i), the molar ratio of the hydroxyl functional group to the deprotonating agent in the compound P3 is 1:1-2; The deprotonating agent is added dropwise to the reaction system containing compound P3 under ice bath, and after the addition is completed, the temperature is returned to room temperature and stirred for 0.5 to 2 hours, and then compound P6 is added dropwise under ice bath and stirred for reaction for 0.1 to 10 hours; The reaction in step (i) is carried out in a solvent, and the solvent is selected from one or a combination of at least two of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, ethylene glycol dimethyl ether, 1,4-dioxane, toluene, benzene, diethyl ether, methyl tert-butyl ether, n-hexane or cyclohexane.

7. 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 polymerizable monomer according to claim 1; Component d) other polymerizable monomers; Component e) photosensitive initiation system; Component f) chain transfer agent; Component g) optional catalyst; Component h) optional additives.

8. The photopolymer holographic recording medium according to claim 7, 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%.

9. The photopolymer holographic recording medium according to claim 7, 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%.

10. The photopolymer holographic recording medium according to claim 7, wherein Based on 100% of the total weight of the photopolymer holographic recording medium, the content of the component c) is 1 to 30%.

11. The photopolymer holographic recording medium according to claim 7, 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%.

12. The photopolymer holographic recording medium according to claim 7, wherein The photosensitive initiation system includes a combination of a photoinitiator and a photosensitizer; the mass ratio of the photosensitizer to the photoinitiator is 0.001-1:0.1-3; The content of 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 thiol 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%.

13. 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 7 to 12.

14. 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 7 to 12.

15. An optical display device, characterized in that: The optical display device comprises the photopolymer holographic recording medium according to any one of claims 7 to 12, the holographic grating according to claim 13, or the holographic optical element according to claim 14.

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