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CN-122010802-A - Optical monomer, holographic recording medium, preparation method and related device

CN122010802ACN 122010802 ACN122010802 ACN 122010802ACN-122010802-A

Abstract

The application discloses an optical monomer, a holographic recording medium, a preparation method and a related device, wherein the structural general formula of the optical monomer is shown as G1 and G2, the refractive index of the monomer is high, the preparation method is simple, and furthermore, the optical monomer with the structure is introduced into a photopolymer type holographic recording medium, so that the holographic recording medium with high sensitivity and high diffraction efficiency is obtained.

Inventors

  • GUO BIN
  • GUAN JIAN
  • WANG ZHAOMIN

Assignees

  • 珠海莫界科技有限公司

Dates

Publication Date
20260512
Application Date
20251225

Claims (20)

  1. 1. An optical monomer is characterized by having any one of the following structural formulas: 、 ; Wherein R 1 represents R 2 represents 、 Or (b) R 3 represents H, C 1 -C 4 alkyl, R 4 represents hydrogen or methyl, R 5 represents C 1 -C 4 alkyl, n=1 to 10, and n is a positive integer.
  2. 2. The optical monomer of claim 1, wherein the optical monomer is a compound having the structural formula: ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; wherein n=1 to 10, and n is a positive integer.
  3. 3. A method of preparing the optical monomer of claim 1, comprising: Dissolving a compound M1 and an acid reagent in an organic solvent, performing a first treatment operation, and then adding a compound M2 for reaction to obtain a compound P1; Reducing the compound P1 to obtain a compound P2; Dissolving a compound M3 and an acid reagent in an organic solvent, performing a first treatment operation, and then adding the compound P2 for reaction to obtain a compound P3; Wherein the first treatment operation comprises at least a heating operation and a stirring operation, and the compound M1 is selected from compounds having the following structural formula: 、 the structural formula of the compound M2 is shown as follows: the structural formula of the compound P1 is shown as follows: 、 ; The structural formula of the compound P2 is shown as follows: 、 ; The structural general formula of the compound M3 is shown as follows , The structural general formula of the compound P3 is shown as follows: 、 and R 3 represents H, C 1 -C 4 alkyl, R 5 represents C 1 -C 4 alkyl.
  4. 4. A method for preparing an optical monomer according to claim 3, wherein the reduction of the compound P1 to the compound P2 comprises the steps of: Dissolving the compound P1 in a first solvent, adding thionyl chloride, and performing a first treatment operation to obtain an intermediate I; and under the hydrogen environment, dissolving the intermediate I, pd/BaSO 4 catalyst and a quinoline-S inhibitor in dimethylbenzene for reaction to obtain the compound P2.
  5. 5. The method for producing an optical monomer according to claim 4, wherein the first solvent is one or more selected from the group consisting of methylene chloride, petroleum ether, n-hexane, cyclohexane, benzene, toluene, and chloroform; and/or the ratio of the volume of the first solvent to the mass of the compound P1 is 5 in mL/g. And/or the ratio of the volume of the xylene solvent to the mass of the intermediate I is 5, in mL/g. And/or the mass of the Pd/BaSO 4 catalyst is 10wt% -20 wt% of the mass of the intermediate I. And/or the mass of the quinoline-S inhibitor is 1 wt% -2 wt% of that of the Pd/BaSO 4 catalyst.
  6. 6. The method for preparing an optical monomer according to claim 3, wherein the optical monomer has a general structural formula of G1, R 2 represents When in use, the method comprises the following steps: Dissolving the compound P3 and an acid binding agent in an organic solvent, and adding a compound M4 for reaction to obtain the optical monomer G1, wherein the compound M4 is acryloyl chloride or methacryloyl chloride; or the optical monomer has a structural general formula of G1, and R 2 represents Or (b) When in use, the method comprises the following steps: And dissolving the compound P3 in a second solvent, performing a second treatment operation, adding a deprotonating agent, and adding a compound M5 after a period of time to obtain the optical monomer G1, wherein the second treatment operation at least comprises a cooling operation and a stirring operation, and the compound M5 is 3-bromo-1-propylene or 3-bromo-1-propyne.
  7. 7. The method for preparing an optical monomer according to claim 3, wherein when the structural formula of the optical monomer is G2, the method further comprises the steps of: dissolving the compound P3 in a second solvent, performing a second treatment operation, adding a deprotonating agent, and adding a compound M6 after a period of time to obtain a compound P4; wherein the second treatment operation at least comprises a cooling operation and a stirring operation, and the structural general formula of the compound M6 is as follows: The structural general formula of the compound P4 is as follows: 、 n is a positive integer, and n=0 to 10.
  8. 8. The method for preparing an optical monomer according to claim 7, wherein the optical monomer has a general structural formula of G2, and R 2 represents When in use, the method further comprises the following steps: Dissolving the compound P4 and an acid binding agent in an organic solvent, and adding the compound M4 to react to obtain the optical monomer G2, wherein the compound M4 is acryloyl chloride or methacryloyl chloride; or the optical monomer has a structural general formula of G2, and R 2 represents Or (b) When in use, the method comprises the following steps: and dissolving the compound P4 in a second solvent, performing a second treatment operation, adding a deprotonating agent, and adding a compound M5 after a period of time to obtain the optical monomer G2, wherein the second treatment operation at least comprises a cooling operation and a stirring operation, and the compound M5 is 3-bromo-1-propylene or 3-bromo-1-propyne.
  9. 9. The method according to claim 3, wherein the organic solvent is one or more selected from the group consisting of methanol, ethanol, petroleum ether, methylene chloride, chloroform, ethyl acetate, tetrahydrofuran, acetonitrile, benzene, toluene, N-dimethylformamide, dimethyl sulfoxide, dimethoxyethane, 1, 4-dioxane, N-hexane, cyclohexane and chloroform; And/or the acid reagent is selected from one or more of p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, camphorsulfonic acid, naphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, sulfosalicylic acid, citric acid, acetic acid, formic acid, phosphoric acid, anhydrous hydrogen peroxide, tetrafluoroboric acid, trifluoroacetic acid, pentafluoroacetic acid, heptafluoropropionic acid and phosphoric acid; And/or the molar ratio of the compound M1 to the acid reagent to the compound M2 is (4-4.8): 2-4): 1; And/or the molar ratio of the compound M3 to the acid reagent to the compound P2 is (8-9.6): 4-8): 1.
  10. 10. The method according to claim 6 or 8, wherein the acid binding agent is selected from triethylamine, pyridine, N Diisopropylethylamine, 4 One or more of dimethylaminopyridine, tetrabutylammonium bromide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium acetate, sodium hydroxide, potassium hydroxide, calcium oxide and potassium tert-butoxide; And/or the second solvent is selected from one or more of petroleum ether, dichloromethane, chloroform, ethyl acetate, tetrahydrofuran, acetonitrile, benzene, toluene, N-dimethylformamide, dimethyl sulfoxide, dimethoxyethane and 1, 4-dioxane; And/or the deprotonating agent is selected from one or more of n-butyllithium, tert-butyllithium, phenyllithium, sodium hydride, potassium hydride, sodium amide, potassium amide, sodium bis (trimethylsilyl) amide, lithium diisopropylamide, potassium hydroxide, sodium methoxide, sodium tert-butoxide, potassium tert-butoxide, triethylamine, 1, 5-diazabicyclo [4.3.0] non-5-ene, 1, 8-diazabicyclo [5.4.0] undec-7-ene, tetramethylsilyl triflate, potassium phosphate, potassium carbonate, sodium carbonate and sodium bicarbonate.
  11. 11. A photopolymer type hologram recording medium characterized in that the raw material thereof comprises the following component a Component h); component a) a compound having a plurality of isocyanate-reactive functional groups; component b) a polyisocyanate-based compound; Component c) an optical monomer; component d) a polymerizable monomer; Component e) a photoinitiating system; Component f) a chain transfer agent; component g) optionally a catalyst; component h) optionally additives; wherein the optical monomer is at least one of the optical monomers G1 or G2 according to claim 1.
  12. 12. The photopolymer holographic recording medium of claim 11, wherein the composition and content of the photopolymer holographic recording medium is as follows: Component a) 10 wt% -50 wt% of a compound having a plurality of isocyanate-reactive functional groups; 10 wt% -50 wt% of a component b) polyisocyanate-based compound; Component c) optical monomers 1 wt% -30 wt%; Component d) 10 wt% -40% wt% of polymerizable monomer; Component e) photoinitiating system 0.1 wt% -3 wt%; component f) 0.1 wt% -3: 3 wt% of chain transfer agent; component g) catalyst 0.1 wt% -5 wt%; The component h) is 0.1 wt% -10 wt% of additive.
  13. 13. The photopolymer type hologram recording medium according to claim 11, wherein the optical monomer accounts for 0.1 wt% -30 wt% of the entire photopolymer type hologram recording medium; And/or the isocyanate-reactive functional groups are hydroxyl groups, the molar ratio of hydroxyl groups in the component a) compound having a plurality of isocyanate-reactive functional groups to isocyanate functional groups in the component b) polyisocyanate-based compound being 1:1.
  14. 14. The photopolymer holographic recording medium of claim 11, wherein the isocyanate reactive functional groups are hydroxyl groups, the compound having a plurality of isocyanate reactive functional groups comprises a compound having a refractive index less than or equal to a first refractive index threshold and having two or more hydroxyl functional groups, the first refractive index threshold being any value between 1.5 and 1.55; And/or the polyisocyanate-based compound includes a compound having a refractive index less than or equal to a second refractive index threshold value and having two or more isocyanate groups, the second refractive index threshold value being any value between 1.5 and 1.55; And/or the polymerizable monomer is selected from at least one of alkenyl naphthalene compounds, alkenyl anthracene compounds, alkenyl benzene compounds, acrylic compounds, methacrylic compounds, N-vinyl pyrrole, N-vinyl carbazole, N-vinyl imidazole, N-vinyl indole, N-vinyl pyrrolidone and trans-N-3-acetylenebutenylcarbazole; and/or, the photoinitiating system comprises a photosensitizer and a photoinitiator; and/or the chain transfer agent is a mercaptan compound; And/or the catalyst is a tertiary amine catalyst and an organic metal catalyst; And/or the additive comprises at least one of an antifoaming agent, a leveling agent, a plasticizer and a water scavenger.
  15. 15. The photopolymer hologram recording medium according to claim 14, wherein the compound having a plurality of isocyanate-reactive functional groups comprises at least one of tetraethylene glycol, trimethylolethane, glycerol, triethanolamine, a polyester polyol having a molecular weight of 200 to 2000, a polycarbonate polyol, a polyether polyol; And/or the polyisocyanate-based compound comprises at least one of hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, (2, 4, 6-trioxytriazine-1, 3,5 (2 h,4h,6 h) -tri-yl) tris (hexamethylene) isocyanate, butane-1, 4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate; And/or the chain transfer agent comprises at least one of dodecyl mercaptan, mercaptoethanol, hexanethiol, phenethyl mercaptan, 5- (4-pyridyl) -1,3, 4-oxadiazole-2-thiol, 4-methyl-4H-1, 2, 4-triazole-3-thiol; And/or the catalyst comprises at least one of triethylenediamine, bis (dimethylaminoethyl) ether, dimethylethanolamine, 2- (2-dimethylamino-ethoxy) ethanol, trimethylhydroxyethyl-propylenediamine, N-bis (dimethylaminopropyl) isopropanolamine, dibutyltin dilaurate, stannous octoate, potassium carboxylate catalysts, and bismuth carboxylate catalysts.
  16. 16. The photopolymer type hologram recording medium according to claim 15, wherein the photosensitizer comprises at least one of a cyanine dye, a fluorescein dye, a coumarin ketone dye, a nitrogen-containing aromatic heterocyclic compound, an aromatic amine compound, and a benzylidene cycloalkanone compound; The photoinitiator comprises aromatic ketone compounds, benzoin and derivatives thereof, benzil ketal, acyl phosphine oxide, aryl ammonium borate, chromium salt, aryl diazonium salt, onium salt, organic metal compound or at least one of the compounds; The mass ratio of the photosensitizer to the photoinitiator is (0.001-1) to (0.1-3).
  17. 17. The photopolymer type hologram recording medium according to claim 15, wherein the antifoaming agent is a silicone antifoaming agent and/or a polymer type antifoaming agent containing no silicone, the antifoaming agent being 3 wt% or less of the photopolymer type hologram recording medium; And/or the leveling agent is an organosilicon surface auxiliary agent, and the content of the leveling agent in the photopolymer type holographic recording medium is less than or equal to 3 wt%; And/or the plasticizer is at least one selected from toluene, xylene, dimethylformamide, dimethylacetamide, glycerin and phthalate, and the plasticizer accounts for less than or equal to 3 wt% of the content of the photopolymer type holographic recording medium; And/or the water remover comprises at least one of p-toluenesulfonyl isocyanate and triethyl orthoformate, and the content of the water remover in the photopolymer type holographic recording medium is less than or equal to 3wt percent.
  18. 18. A method for producing a photopolymer holographic recording medium according to any of the claims 11-17, wherein, Weighing the compound with a plurality of isocyanate-reactive functional groups, the polyisocyanate-based compound, the optical monomer, the polymerizable monomer, the photoinitiating system, the chain transfer agent, the catalyst and the additive in a container, and sufficiently stirring until the mixture is dissolved to form a mixture solution; filtering the mixture solution using a filter membrane to obtain a first solution; and coating the first solution on a substrate, and drying to obtain the photopolymer type holographic recording medium.
  19. 19. The method according to claim 18, wherein the drying is performed in a dark room having a humidity of 10% -85% and a temperature of 20 ℃ -50 ℃.
  20. 20. A volume hologram recording grating, wherein the material comprises a photopolymer hologram recording medium according to any one of claims 11 to 17.

Description

Optical monomer, holographic recording medium, preparation method and related device Technical Field The application relates to the technical field of holographic materials, in particular to an optical monomer, a holographic recording medium, a preparation method and a related device. Background The photopolymer used for manufacturing the holographic recording medium generally comprises photosensitive dye, initiator, chain transfer agent, writing monomer, film forming resin, plasticizer and the like, and the photopolymer is used for realizing holographic recording by forming a phase type holographic grating with modulated refractive index with the film forming resin after polymerizing the writing monomer by illumination. When the concentration of the writing monomer in the coherent light area is reduced due to consumption of polymerization, unreacted writing monomer in the coherent dark area is quickly migrated to the coherent light area, and film-forming resin in the coherent light area is extruded to the coherent dark area, so that the refractive index of the coherent light area is close to that of the writing monomer, and the refractive index of the coherent dark area is close to that of the film-forming resin, so that the phase type holographic grating with refractive index modulation is formed. However, the existing photopolymer usually has obvious volume shrinkage after exposure, so that the recorded grating is deviated, and thus the recorded grating obtained by exposure is inconsistent with the theoretical design, although the dendritic monomer can be added to effectively reduce the volume shrinkage of the photopolymer, the currently available dendritic monomer is not much, and the refractive index is usually lower than 1.65, so that the refractive index modulation degree of the prepared recorded grating is lower (delta n < 0.07), further the regulation capability of the recorded grating on incident light is reduced, the light energy loss is excessive, the diffraction efficiency of an optical device is low, the imaging picture is unclear, and the like. Disclosure of Invention The application aims to provide an optical monomer, a holographic recording medium, a preparation method and a related device, wherein the optical monomer has a high refractive index so as to solve the problem that a recorded grating is offset due to volume shrinkage of a photopolymer holographic recording medium after exposure, and further improve the holographic performance of the holographic recording grating. In a first aspect, the present application provides an optical monomer having a structural formula shown in any one of the following formulas: ;; Wherein R 1 represents R 2 represents、、R 3 represents H,C 1-C4 alkyl, R 4 represents hydrogen or methyl, R 5 represents C 1-C4 alkyl, n=1 to 10, and n is a positive integer. From the above technical solution, it can be seen that the optical monomer provided in the first aspect of the present application is a dendritic monomer, which has a structure of a plurality of aromatic mercaptal, and the high electron polarizability and molecular stacking effect of sulfur atoms have a significant influence on the refractive index of the monomer. Moreover, based on the presence of multiple benzene rings, the conjugation effect will superimpose the polarization of sulfur, giving the monomer a higher refractive index, greater than 1.70 and less than 1.75. In a second aspect, the present application provides a method for preparing the above optical monomer, comprising: Dissolving a compound M1 and an acid reagent in an organic solvent, performing a first treatment operation, and then adding a compound M2 for reaction to obtain a compound P1; Reducing the compound P1 to obtain a compound P2; Dissolving a compound M3 and an acid reagent in an organic solvent, performing a first treatment operation, and then adding the compound P2 for reaction to obtain a compound P3; Wherein the first treatment operation comprises at least a heating operation and a stirring operation, and the compound M1 is selected from compounds having the following structural formula: 、 the structural formula of the compound M2 is shown as follows: , the structural formula of the compound P1 is shown as follows: 、, The structural formula of the compound P2 is shown as follows: 、, The structural general formula of the compound M3 is shown as follows , The structural general formula of the compound P3 is shown as follows:、 and R 3 represents H, C 1-C4 alkyl, R 5 represents C 1-C4 alkyl. According to the technical scheme, the preparation method of the optical monomer provided by the second aspect of the application has the advantages of simple synthesis method, short route, low-cost and easily-obtained required raw materials and easiness in large-scale production. In a third aspect, the present application provides a photopolymer type holographic recording medium comprising the following component aComponent h); component a) a