Phenylene sulfide monomer as well as preparation method and application thereof

Abstract

The invention provides a phenyl sulfide monomer as well as a preparation method and application thereof. The phenyl sulfide monomer has a structure as shown in a formula G1. The phenyl sulfide monomer has a high refractive index, is presented in a liquid form at room temperature, and is easy to diffuse and migrate in an exposure process, and the photopolymer material prepared from the phenyl sulfide monomer has excellent properties of high sensitivity, high recording grating diffraction efficiency, high refractive index modulation degree and the like.

Description

Technical Field

[0001] This application belongs to the field of holographic materials technology, specifically relating to a phenyl sulfide monomer, its preparation method, and its application. Background Technology

[0002] Photopolymer materials used for holographic recording mainly include photosensitive dyes, initiators, chain transfer agents, recording monomers, film-forming resins, and plasticizers. Holographic recording is achieved by using light to polymerize the monomers, which then combine with the film-forming resin to form a phase-type holographic grating with refractive index modulation. In the coherent bright region, monomer polymerization consumes and reduces concentration, while in the coherent dark region, monomers hardly react. The difference in monomer concentration between the bright and dark regions causes monomers in the dark region to migrate towards the bright region. Simultaneously, the film-forming resin in the bright region is squeezed into the dark region. Ultimately, the refractive index of the bright region approaches the refractive index of the polymer, and the refractive index of the dark region approaches the refractive index of the film-forming resin, thus forming a phase-type volume holographic grating with refractive index modulation.

[0003] To improve the performance of photopolymers, a lower refractive index is generally required for the base resin and a higher refractive index for the recording monomer. However, the refractive index of the recording monomers currently used in photopolymers is typically below 1.6, resulting in a small refractive index difference between the recording monomer and the film-forming resin (usually 0.1~0.2). Therefore, increasing the refractive index difference between the two is beneficial for achieving higher performance in photopolymers. Sulfur-containing compounds often have high refractive indices, with diphenyl sulfide being a commonly used structure among high-refractive-index monomers. However, due to the strong transient dipole-dipole interactions between diphenyl sulfide molecules and the long CS bond allowing for a more favorable spatial arrangement of the two benzene rings, diphenyl sulfide exhibits a highly symmetrical planar structure. Recording monomers containing this structure are often solid, which limits the diffusion and migration of the monomer during exposure.

[0004] Therefore, developing a liquid phenyl sulfide monomer with high refractive index and easy diffusion and migration during the exposure process is an urgent problem to be solved in this field. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the purpose of this application is to provide a phenyl sulfide monomer, its preparation method, and its application. The phenyl sulfide monomer has a high refractive index and exists in a liquid state at room temperature, exhibiting easy diffusion and migration during exposure. The photopolymer material prepared from it possesses excellent properties such as high sensitivity, high recording grating diffraction efficiency, high refractive index modulation, and low exposure.

[0006] To achieve this objective, the following technical solution is adopted in this application:

[0007] In a first aspect, this application provides a phenyl sulfide monomer having the structure shown in formula G1:

[0008] .

[0009] In formula G1, R1 is selected from C4-C10 straight-chain alkyl groups, and at least two non-adjacent -CH2- groups in the C4-C10 straight-chain alkyl groups are replaced by -S- groups; R2 is selected from C2-C4 alkenyl, C2-C4 alkynyl, ... Any one of them; A1 is selected from H or C1~C4 straight-chain or branched alkyl; the wavy line indicates the linking site.

[0010] In this application, the phenyl sulfide monomers are produced by elongating the alkyl chains within the diphenyl sulfide structure, disrupting its highly symmetrical planar structure, and allowing the monomers to exist in a liquid state at room temperature, which is beneficial for the diffusion and migration of the monomers. Furthermore, sulfur atoms are introduced into the alkyl chains to ensure that the phenyl sulfide monomers have a high refractive index and to avoid a decrease in refractive index caused by the introduction of alkyl chains. The phenyl sulfide monomers adopt a specific structural design that combines high refractive index with good diffusion and migration properties. When used in photopolymer holographic recording media, they can improve the sensitivity, recording grating diffraction efficiency, and refractive index modulation of the photopolymer holographic recording media, while reducing the exposure.

[0011] In this application, the C4 to C10 straight-chain alkyl group can be, for example, a C5, C6, C7, C8, or C9 straight-chain alkyl group, including but not limited to n-pentyl, n-hexyl, and n-octyl.

[0012] In this application, C2-C4 alkenyl groups can be, for example, vinyl, propenyl, or butenyl; C2-C4 ynyl groups can be, for example, ethynyl, propynyl, or butynyl; and C1-C4 straight-chain or branched alkyl groups can be, for example, methyl, ethyl, n-propyl, or isopropyl.

[0013] In this application, the phenyl sulfide monomer has any one of the structures shown in formula G11 and formula G12.

[0014] .

[0015] R1 and R2 are each independently selected from the same range of constraints as Equation G1.

[0016] In this application, in formula G1, R1 is selected from... or R2 is selected from Any one of them; A1 is selected from H or methyl; the wavy line indicates the connection site.

[0017] In this application, the phenyl sulfide monomers are selected from any one of the following compounds.

[0018]

[0019] Secondly, this application provides a method for preparing phenyl sulfide monomers according to the first aspect, the method comprising the following steps:

[0020] (1) React compound P1 with compound P2 to obtain compound P3;

[0021] (2) Reaction of compound P3 with compound L1 yields a phenyl sulfide monomer with the structure shown in formula G1.

[0022] Compound P1 has the structure shown in Formula I: Formula I.

[0023] Compound P2 has the structure shown in Formula II: Formula II; R4 is selected from -S- or .

[0024] Compound P3 has the structure shown in Formula III: Formula III.

[0025] Compound L1 has the structure shown in Formula VI: X-R2, where X is selected from halogens.

[0026] In this application, the halogen includes any one of F, Cl, Br, and I.

[0027] In this application, the molar ratio of compound P1 to compound P2 in step (1) is (2~3):1, for example, it can be 2.2:1, 2.4:1, 2.6:1, 2.8:1, etc.

[0028] In this application, the raw materials for the reaction in step (1) further include at least one of silver nitrate, potassium persulfate, and solvent; based on the molar content of compound P2 as 1 mol, the molar content of silver nitrate is 2~3 mol, for example, it can be 2.2 mol, 2.4 mol, 2.6 mol, 2.8 mol, etc.; the molar content of potassium persulfate is 3~9 mol, for example, it can be 4 mol, 5 mol, 6 mol, 7 mol, 8 mol, etc.; the volume of solvent is 2~10 L, for example, it can be 4 L, 6 L, 8 L, etc.

[0029] In this application, the solvent for the reaction in step (1) includes a mixed solution of acetonitrile and water; the volume ratio of acetonitrile to water can be 1:1.

[0030] In this application, the temperature of the reaction in step (1) is 40~100℃, for example, it can be 50℃, 60℃, 70℃, 80℃, 90℃, etc.; the time is 1~36 h, for example, it can be 2 h, 6 h, 10 h, 14 h, 18 h, 22 h, 26 h, 30 h, 34 h, etc.

[0031] In this application, after the reaction in step (1) is completed, a post-processing step is also included; the post-processing includes rotary evaporation, column chromatography purification, etc.

[0032] In this application, the molar ratio of compound L1 to compound P3 in step (2) is (2~4):1, for example, it can be 2.2:1, 2.5:1, 2.8:1, 3:1, 3.2:1, 3.5:1, 3.8:1, etc.

[0033] In this application, when R2 is selected from C2-C4 alkenyl or C2-C4 alkynyl, the molar ratio of compound L1 to compound P3 is (2-3):1; when R2 is selected from... The molar ratio of compound L1 to compound P3 is (2~4):1.

[0034] In this application, the reaction in step (2) includes: pre-reacting compound P3 with a deprotonating agent or an acid-binding agent in the presence of a solvent, and then adding compound L1 to react therein.

[0035] In this application, with the molar content of compound P3 as 1 mol, the molar content of the deprotonating agent is 2-3 mol, for example, 2.2 mol, 2.4 mol, 2.6 mol, 2.8 mol, etc.; the molar content of the acid-binding agent is 3-5 mol, for example, 3.2 mol, 3.5 mol, 3.8 mol, 4 mol, 4.2 mol, 4.5 mol, 4.8 mol, etc.

[0036] In this application, the solvent for the reaction in step (2) can be a commonly used solvent in the art, including but not limited to one or more of ethanol, petroleum ether, dichloromethane, chloroform, ethyl acetate, tetrahydrofuran, toluene, acetonitrile, N,N-dimethylformamide or dimethyl sulfoxide.

[0037] In this application, the deprotonating agent used in step (2) includes, but is not limited to, one or more of the following: n-butyllithium, tert-butyllithium, phenyllithium, sodium hydride, potassium hydride, sodium amino, potassium amino, sodium bis(trimethylsilyl)amino, potassium tert-butoxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, triethylamine, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, and tetramethylsilyltrifluoromethanesulfonate.

[0038] In this application, the acid-binding agent used in step (2) includes, but is not limited to, one or more of pyridine, triethylamine, N,N-diisopropylethylamine, 4-dimethylaminopyridine, sodium carbonate, potassium carbonate, sodium acetate, sodium hydroxide, potassium hydroxide, calcium oxide, and potassium tert-butoxide.

[0039] In this application, when R2 is selected from C2~C4 alkenyl or C2~C4 alkynyl, a deprotonating agent is added for pre-reaction. The temperature of the pre-reaction and the reaction in step (2) is independently about 0°C. The time of the pre-reaction and the reaction is independently 0.5~10h, for example, 1h, 2h, 4h, 6h, 8h, etc.

[0040] In this application, when R2 is selected from... When adding an acid-binding agent, a pre-reaction is carried out. The pre-reaction in step (2) is carried out in an ice bath for 5 to 20 minutes. The reaction temperature is about 0°C. The reaction time is 0.5 to 2 hours, for example, 1 hour or 1.5 hours.

[0041] Thirdly, this application provides a photopolymer-type holographic recording medium, the photopolymer-type holographic recording medium comprising a writing monomer, the writing monomer comprising the phenyl sulfide monomers described in the first aspect.

[0042] In this application, the photopolymer-type holographic recording medium comprises the following components, by weight percentage:

[0043]

[0044] It should be noted that photopolymer holographic recording media typically contain a low-refractive-index base resin and a high-refractive-index recording monomer (or writing monomer). In this application, compounds with multiple isocyanate reactive functional groups and polyisocyanate group compounds can form the base resin.

[0045] In this application, the compound having multiple isocyanate reactive functional groups is 10-40%, for example, it can be 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, etc.

[0046] In this application, the compound having multiple isocyanate reactive functional groups includes hydroxyl groups; preferably, it is a compound with a low refractive index and two or more hydroxyl functional groups; more preferably, it is one or more of tetraethylene glycol, trimethylolethane, glycerol, triethanolamine, polyester polyols, polycarbonate polyols, and polyether polyols with a number average molecular weight of 200 to 2000.

[0047] In this application, the polyisocyanate group compound is 10-40%, for example, it can be 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, etc.

[0048] In this application, the polyisocyanate-based compound includes compounds with low refractive index and two or more isocyanate groups; more preferably, it is one or more of hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, (2,4,6-trioxotriazine-1,3,5(2H,4H,6H)-triyl)tri(hexamethylene)isocyanate, butane-1,4-diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate.

[0049] In this application, the percentage of individual components written is 1% to 85%, for example, it can be 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, etc.

[0050] In this application, the photoinitiator system is 0.1% to 3%, for example, it can be 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, etc.

[0051] In this application, the photosensitive initiation system includes a photosensitizer and a photoinitiator; the mass ratio of the photosensitizer to the photoinitiator is 0.001~1:0.1~3. Different broadband responses can be achieved by adjusting the type of photosensitizer. However, when a photoinitiator with a suitable wavelength is selected in the raw material of the photopolymer-type holographic recording medium of this application, the photosensitizer may not be added.

[0052] For example, the photosensitizer is a dye with high electron transfer efficiency under light irradiation, including but not limited to one or more of cyanine dyes, fluorescein dyes, coumarin ketone dyes, nitrogen-containing aromatic heterocyclic compounds, aromatic amine compounds, and benzylidene cycloalkanes ketone compounds. Specifically, the photosensitizer includes one or more of the following: neomethylene blue, thionine, basic yellow, pinacyanine chloride, rhodamine 6G, gallium cyanide, ethyl violet, Victoria blue R, azurite blue, methylene blue, Astrazon Orange G, Darrow red, pyrrole red Y, eosin Y, basic red 29, quinaldinium red, crystal violet, ethyl violet, brilliant green, pyrifoliium I, azure A, crystal violet cyanonitrile, and malachite green cyanonitrile.

[0053] In this application, the photoinitiator is an initiator that can be activated by photochemical radiation and initiate a polymerization reaction of the corresponding polymerizable groups. It includes, but is not limited to, one or more of aromatic ketone compounds, benzoin and its derivatives, benzoyl ketals, acylphosphine oxides, ammonium arylboronate, chromium salts, aryl diazonium salts, onium salts, and organometallic compounds. Specifically, the photoinitiator includes one or more of the following: benzophenone, alkylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, anthrone and halogenated benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, diacylphosphine oxide, phenyl dihydroxyacetate, camphorquinone, α-aminoalkylphenyl ketone, α,α-dialkoxyacetophenone, α-hydroxyalkylphenyl ketone, tetrabutylammonium triphenylhexylborate, tetrabutylammonium tri-(3-fluorophenyl)hexylborate, tetrabutylammonium tri-(3-chloro-4-methylphenyl)hexylborate, ferrocene-based compounds, iodonium salts, thiodonium salts, hexaaryldiimidazole, and N-phenylglycine.

[0054] In this application, the chain transfer agent is 0.1% to 3%, for example, it can be 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, etc.

[0055] In this application, the chain transfer agent includes thiol compounds, including but not limited to one or more of dodecyl mercaptan, mercaptoethanol, hexamethylene mercaptan, phenylethyl mercaptan, 5-(4-pyridyl)-1,3,4-oxadiazole-2-thiol, and 4-methyl-4H-1,2,4-triazole-3-thiol.

[0056] In this application, the catalyst is optionally 0.1% to 3%, for example, it can be 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, etc.

[0057] In this application, the catalyst includes tertiary amine catalysts and / or organometallic catalysts, including but not limited to one or more of the following: triethylenediamine, bis(dimethylaminoethyl) ether, dimethylethanolamine, 2-(2-dimethylamino-ethoxy)ethanol, trimethylhydroxyethylpropanediamine, N,N-bis(dimethylaminopropyl)isopropanolamine, dibutyltin dilaurate, stannous octoate, potassium carboxylate catalysts, and bismuth carboxylate catalysts.

[0058] In this application, the additive is optionally 0.1% to 9%, for example, it can be 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 7%, 8%, etc.

[0059] In this application, the additives include one or more of defoamers, leveling agents, plasticizers, and dehydrating agents.

[0060] In this application, when the additive includes an antifoaming agent, the content of the antifoaming agent does not exceed 3% based on the total mass of the photopolymer holographic recording medium.

[0061] In this application, when the additive includes a leveling agent, the content of the leveling agent does not exceed 3% based on the total mass of the photopolymer holographic recording medium.

[0062] In this application, when the additive includes a plasticizer, the content of the plasticizer does not exceed 3% based on the total mass of the photopolymer holographic recording medium.

[0063] In this application, when the additive includes a dehydrating agent, the content of the dehydrating agent does not exceed 3% based on the total mass of the photopolymer holographic recording medium.

[0064] In this application, the defoamer includes silicone defoamers, such as BYK-011, BYK-012, BYK-014, BYK-023, BYK-051N, BYK-085, BYK-1610, BYK-1707, BYK-1740, and BYK-1760 manufactured by BYK Corporation, DC65 and AFE-7820 manufactured by Dow Corning Incorporated, or any mixture of these defoamers in any proportion.

[0065] In this application, the leveling agent includes silicone surface additives, such as BYK-302, BYK-306, BYK-307, BYK-327, BYK-329, BYK-333, BYK-356, BYK-358, BYK-378, BYK-3455, BYK-3566, or any mixture of these surface additives manufactured by BYK Corporation.

[0066] In this application, the plasticizer includes toluene, xylene, dimethylformamide, dimethylacetamide, glycerol, phthalates, or any mixture of these compounds in any proportion.

[0067] In this application, the dehydrating agents include, but are not limited to, p-toluenesulfonyl isocyanate, triethyl orthoformate, CUWR-WB20 dehydrating agent from Guangzhou Yourun Synthetic Materials Co., Ltd., ALT-201 dehydrating agent from Anxiang Elite Chemical Co., Ltd., and PCCI dehydrating agent from Shanghai Luer Chemical Trading Co., Ltd.

[0068] In this application, it is optional to indicate that something may or may not be added.

[0069] In this application, the writing monomer also includes phenyl sulfide monomers having the structure shown in Formula G2.

[0070] .

[0071] In formula G2, R3 is selected from C1-C4 straight-chain or branched alkyl groups; R2 is selected from C2-C4 alkenyl, C2-C4 alkynyl, ... Any one of them; A1 is selected from H or C1~C4 straight-chain or branched alkyl; the wavy line indicates the linking site.

[0072] In this application, the phenyl sulfide monomer having the structure shown in formula G2 has any one of the structures shown in formula G21 and formula G22;

[0073] ;

[0074] R2 and R3 are each independently selected from the same range of constraints as Equation G2.

[0075] In this application, the phenyl sulfide monomer having the structure shown in Formula G2 is selected from any one of the following compounds.

[0076]

[0077] In this application, the method for preparing the phenyl sulfide monomer having the structure shown in Formula G2 includes the following steps:

[0078] (S1) Compound P1 reacts with compound P4 to give compound P5;

[0079] (S2) Reaction of compound P5 with compound L2 yields a phenyl sulfide monomer having the structure shown in formula G2.

[0080] Compound P4 has the structure shown in Formula IV: Formula IV.

[0081] Compound P5 has the structure shown in Formula V: Formula V.

[0082] Compound L2 is X-R2, where X is selected from halogens.

[0083] In this application, the molar ratio of compound P1 to compound P4 in step (S1) is (1~2):1, for example, it can be 1.2:1, 1.4:1, 1.6:1, 1.8:1, etc.

[0084] In this application, the raw materials for the reaction in step (S1) further include at least one of silver nitrate, potassium persulfate, and a solvent; based on the molar content of compound P4 as 1 mol, the molar content of silver nitrate is 0.5~1.5 mol, for example, 0.6 mol, 0.8 mol, 1 mol, 1.2 mol, 1.4 mol, etc.; the molar content of potassium persulfate is 1.5~4.5 mol, for example, 2 mol, 2.5 mol, 3 mol, 3.5 mol, 4 mol, etc.; the volume of the solvent is 2~10 L, for example, 4 L, 6 L, 8 L, etc.

[0085] In this application, the solvent for the reaction in step (S1) includes a mixed solution of acetonitrile and water; the volume ratio of acetonitrile to water can be 1:1.

[0086] In this application, the temperature of the reaction in step (S1) is 40~100℃, for example, it can be 50℃, 60℃, 70℃, 80℃, 90℃, etc.; the time is 1~36 h, for example, it can be 2 h, 6 h, 10 h, 14 h, 18 h, 22 h, 26 h, 30 h, 34 h, etc.

[0087] In this application, after the reaction described in step (S1) is completed, a post-processing step is also included; the post-processing includes rotary evaporation, column chromatography purification, etc.

[0088] In this application, the molar ratio of compound L2 to compound P5 in step (S2) is (1~3):1, for example, it can be 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, etc.

[0089] In this application, when R2 is selected from C2-C4 alkenyl or C2-C4 alkynyl, the molar ratio of compound L2 to compound P5 is (1-2):1; when R2 is selected from... The molar ratio of compound L2 to compound P5 is (1~3):1.

[0090] In this application, the reaction in step (S2) includes: pre-reacting compound P5 with a deprotonating agent or an acid-binding agent in the presence of a solvent, and then adding compound L2 to the solvent to carry out the reaction.

[0091] In this application, with the molar content of compound P5 as 1 mol, the molar content of the deprotonating agent is 1~2 mol, for example, it can be 1.2 mol, 1.4 mol, 1.6 mol, 1.8 mol, etc.; the molar content of the acid-binding agent is 2~4 mol, for example, it can be 2.2 mol, 2.5 mol, 3 mol, 3.5 mol, etc.

[0092] In this application, the solvent for the reaction in step (S2) can be a commonly used solvent in the art, including but not limited to one or more of ethanol, petroleum ether, dichloromethane, chloroform, ethyl acetate, tetrahydrofuran, toluene, acetonitrile, N,N-dimethylformamide or dimethyl sulfoxide.

[0093] In this application, the deprotonating agent used in step (S2) includes, but is not limited to, one or more of the following: n-butyllithium, tert-butyllithium, phenyllithium, sodium hydride, potassium hydride, sodium amino, potassium amino, sodium bis(trimethylsilyl)amino, potassium tert-butoxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, triethylamine, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, and tetramethylsilyltrifluoromethanesulfonate.

[0094] In this application, the acid-binding agent used in step (S2) includes, but is not limited to, one or more of the following: pyridine, triethylamine, N,N-diisopropylethylamine, 4-dimethylaminopyridine, sodium carbonate, potassium carbonate, sodium acetate, sodium hydroxide, potassium hydroxide, calcium oxide, and potassium tert-butoxide.

[0095] In this application, when R2 is selected from C2~C4 alkenyl or C2~C4 alkynyl, a deprotonating agent is added for pre-reaction. The temperature of the pre-reaction and the reaction in step (S2) is independently around 0°C. The time of the pre-reaction and the reaction is independently 0.5~10h, for example, 1h, 2h, 4h, 6h, 8h, etc.

[0096] In this application, when R2 is selected from... When adding an acid-binding agent, a pre-reaction is carried out. The pre-reaction in step (S2) is carried out in an ice bath for 5 to 20 minutes. The reaction temperature is about 0°C. The reaction time is 0.5 to 2 hours, for example, 1 hour or 1.5 hours.

[0097] In this application, the photopolymer-type holographic recording medium includes 1-50% (e.g., 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, etc.) of phenyl sulfide monomers having the structure shown in Formula G1 and 1-35% (e.g., 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 34%, etc.) of phenyl sulfide monomers having the structure shown in Formula G2.

[0098] In this application, the phenyl sulfide monomers having the structure shown in Formula G1 and the phenyl sulfide monomers having the structure shown in Formula G2 have good miscibility. After mixing, the viscosity of the mixed monomers is low, which is also conducive to promoting diffusion and migration. Furthermore, the phenyl sulfide monomers having the structure shown in Formula G2 can effectively adjust the crosslinking density of the polymer, making it difficult for the monomers to separate from the film-forming resin after polymerization. This is beneficial to further improve the sensitivity, recording grating diffraction efficiency, and refractive index modulation of the photopolymer holographic recording medium, while reducing the exposure.

[0099] Fourthly, this application provides a holographic optical element, the raw material of which includes the photopolymer-type holographic recording medium described in the third aspect.

[0100] Fifthly, this application provides an optical device comprising the holographic optical element as described in the fourth aspect.

[0101] The numerical range described in this application includes not only the point values ​​listed above, but also any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of brevity, this application will not exhaustively list the specific point values ​​included in the range.

[0102] Compared with the prior art, the beneficial effects of this application are as follows:

[0103] The phenyl sulfide monomers provided in this application have a specific structural design that combines high refractive index with good diffusion and migration properties. When used in photopolymer holographic recording media, they can improve the sensitivity, recording grating diffraction efficiency, and refractive index modulation of the photopolymer holographic recording media, while reducing the exposure. Attached Figure Description

[0104] Figure 1 Holographic exposure characteristic curves of photopolymer holographic recording media provided in Application Examples 1, 6, 8 and 16 of this application.

[0105] Figure 2 The holographic exposure characteristic curves of the photopolymer holographic recording medium provided in Comparative Application Example 3 of this application are shown. Detailed Implementation

[0106] The technical solution of this application will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely to help understand this application and should not be regarded as specific limitations on this application.

[0107] All materials used in this application are commercially available or prepared using conventional methods, unless otherwise specified.

[0108] Synthesis Example 1

[0109] This synthetic example provides a phenyl sulfide monomer, which is The synthetic route for the phenyl sulfide monomers is shown below.

[0110]

[0111] .

[0112] Specific preparation methods include;

[0113] (1) Compound P1-1 (2.5 equivalents), compound P2-1 (1 equivalent), silver nitrate (2.5 equivalents), and potassium persulfate (6 equivalents) were dissolved in 6 L of a mixed solution of acetonitrile and water (volume ratio 1:1). The mixture was heated to 70 °C and stirred for 12 h. The solvent was removed by rotary evaporation and purified by column chromatography to obtain compound P3-1.

[0114] (2) Dissolve 1 equivalent of compound P3-1 in 6 L of dichloromethane, stir until homogeneous, lower the temperature to 0 °C, slowly add 2.5 equivalents of the deprotonating agent tert-butyllithium, stir for 5 h, and after the reaction is complete, add 2.5 equivalents of compound allyl bromide dropwise, and continue stirring for 5 h after the addition is complete. Quench the reaction by slowly adding dilute hydrochloric acid, remove excess solvent by rotary evaporation, and separate by column chromatography to obtain the target product G1-1, which is the phenyl sulfide monomer.

[0115] The structure of compound G1-1 was characterized using proton NMR and carbon NMR spectrometry, and the results are as follows:

[0116] 1H NMR (600 MHz, CDCl3) δ 7.41 – 7.08 (m, 4H), 7.00 – 6.74 (m, 4H), 6.03 (tt, J = 13.4, 6.2 Hz, 2H), 5.59 – 5.18 (m, 4H), 4.52 (dt, J = 6.2, 1.1Hz, 4H), 3.80 (s, 4H).

[0117] 13C NMR (151 MHz, CDCl3) δ 157.21, 133.80, 132.05, 130.86, 117.67,115.81, 69.63, 37.43.

[0118] Synthesis Example 2

[0119] This synthetic example provides a phenyl sulfide monomer, which is The synthetic route for the phenyl sulfide monomers is shown below.

[0120]

[0121] .

[0122] The specific synthesis method differs from Example 1 only in the raw materials. Specifically, P2-1 is replaced with an equimolar amount of P2-2, and allyl bromide is replaced with an equimolar amount of propargyl bromide. All other raw materials, amounts, and process parameters are the same as in Example 1.

[0123] The structure of compound G1-2 was characterized using proton NMR and carbon NMR spectroscopy, and the results are as follows:

[0124] 1H NMR (600 MHz, CDCl3) δ 7.57 – 7.12 (m, 4H), 7.03 – 6.70 (m, 4H), 4.79 (d, J = 2.9 Hz, 4H), 3.81 (s, 4H), 3.55 (t, J = 3.0 Hz, 2H), 2.87 (s,4H).

[0125] 13C NMR (151 MHz, CDCl3) δ 156.16, 132.34, 130.17, 116.29, 79.02, 76.01, 56.75, 37.68, 33.56.

[0126] Synthesis Example 3

[0127] This embodiment provides a phenyl sulfide monomer, which is The synthetic route for the phenyl sulfide monomers is shown below.

[0128]

[0129] .

[0130] Specific synthesis methods include:

[0131] (1) Compound P1-2 (2.5 equivalents), compound P2-1 (1 equivalent), silver nitrate (2.5 equivalents), and potassium persulfate (6 equivalents) were dissolved in 6 L of a mixed solution of acetonitrile and water (volume ratio 1:1). The mixture was heated to 70 °C and stirred for 12 h. The solvent was removed by rotary evaporation and purified by column chromatography to obtain compound P3-3.

[0132] (2) Under ice bath conditions, 1 equivalent of compound P3-3 and 4 equivalents of the acid-binding agent triethylamine were dissolved in 6 L of organic solvent dichloromethane. After stirring for 10 min, 3 equivalents of acryloyl chloride were added dropwise to the mixed solution of compound P3-3 and the acid-binding agent at 0 °C. The reaction was stirred for 1 h. After the reaction was complete, dilute hydrochloric acid was added dropwise to remove excess acryloyl chloride. The mixture was washed successively with saturated NaCl solution, saturated NaHCO3 solution, and deionized water. The organic phase was dried over anhydrous sodium sulfate, and excess solvent was removed by rotary evaporation. The target monomer G1-3 was obtained by column chromatography, which yielded the phenyl sulfide monomer.

[0133] The structure of compound G1-3 was characterized using proton NMR and carbon NMR spectroscopy, and the results are as follows:

[0134] 1H NMR (600 MHz, CDCl3) δ 7.36 (t, J = 7.4 Hz, 2H), 7.29 (dt, J =7.5, 1.6 Hz, 2H), 7.23 – 7.18 (m, 4H), 6.15 – 6.03 (m, 2H), 5.84 (s, 2H), 5.81 (d, J = 0.7 Hz, 2H), 3.82 (s, 4H).

[0135] 13C NMR (151 MHz, CDCl3) δ 165.26, 151.37, 137.27, 131.91, 129.69, 127.69, 125.93, 120.57, 119.53, 37.42.

[0136] Synthesis Example 4

[0137] This synthetic example provides a phenyl sulfide monomer, which is The synthetic route for the phenyl sulfide monomers is as follows.

[0138]

[0139] .

[0140] Specific synthesis methods include:

[0141] (S1) Compound P1-2 (1.5 equivalents), compound P4 (1 equivalent), silver nitrate (1 equivalent), and potassium persulfate (3 equivalents) were dissolved in 6 L of a mixed solution of acetonitrile and water (volume ratio 1:1). The mixture was heated to 70 °C and stirred for 12 h. The solvent was removed by rotary evaporation, and the mixture was purified by column chromatography to obtain compound P5-1.

[0142] (S2) Under ice bath conditions, 1 equivalent of compound P5-1 and 3 equivalents of the acid-binding agent triethylamine were dissolved in 6 L of organic solvent dichloromethane. After stirring for 10 min, 2 equivalents of methacryloyl chloride were added dropwise to the mixed solution of compound P5-1 and the acid-binding agent at 0 °C, and the reaction was stirred for 1 h. After the reaction was complete, dilute hydrochloric acid was added dropwise to remove excess methacryloyl chloride. The mixture was washed successively with saturated NaCl solution, saturated NaHCO3 solution, and deionized water. The organic phase was dried over anhydrous sodium sulfate, and excess solvent was removed by rotary evaporation. Column chromatography was used to separate the target monomer G2-1, which is the phenyl sulfide monomer.

[0143] This application provides exemplary methods for synthesizing the above-mentioned phenyl sulfide monomers. Other phenyl sulfide monomers for which no specific synthesis method is provided can also be prepared by similar methods, simply by replacing the raw materials. These methods will not be elaborated here. Only the specific structures and refractive index test results of the phenyl sulfide monomers are given, as shown in Table 1. The refractive index was obtained by measuring the Abbe refractive index, and the viscosity was obtained by measuring the viscosity at 25°C using a viscometer.

[0144] Table 1

[0145]

[0146]

[0147] As shown in Table 1, the phenyl sulfide monomers with the structure shown in Formula G1 provided in this application have a refractive index ≥1.64 and are liquid at room temperature.

[0148] Application Examples 1-4

[0149] Application Examples 1-4 provide a photopolymer holographic recording medium, the composition of which, by mass percentage, is shown in Table 2.

[0150] Among them, the photoinitiator system 1 is a new methylene blue and benzophenone with a mass ratio of 0.5:1.

[0151] The photoinitiator system 2 consists of crystal violet and camphorquinone in a mass ratio of 0.1:3.

[0152] The photoinitiator system 3 consists of eosin Y and N-phenylglycine in a mass ratio of 0.3:2.

[0153] The defoamer is BYK-011 manufactured by BYK Corporation; the leveling agent is BYK-302 manufactured by BYK Corporation; and the plasticizer is dibutyl phthalate.

[0154] The preparation method of the photopolymer holographic recording medium includes: mixing the components evenly.

[0155] Table 2

[0156]

[0157] The only difference between Application Examples 5-18 and Comparative Application Examples 1-3 and Application Example 1 is the type of phenyl sulfide monomer, as shown in Table 3; the other components, dosages, and preparation methods are the same as in Application Example 1.

[0158] Table 3

[0159]

[0160] Performance testing

[0161] The testing method for the performance of holographic recording media includes the following steps:

[0162] For the holographic recording medium, solid-state lasers with wavelengths of 633nm, 457nm, 532nm, and 633nm were used as light sources according to their photosensitive wavelengths. After passing through a beam expander, beam splitter, and half-wave plate, two beams with the same intensity and a diameter of 8 mm were obtained. The two beams were intersected and exposed within the prepared holographic recording medium at an intensity of 3mW / cm². 2 The detection light source uses a 785 nm 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 by formulas (1) to (3).

[0163]

[0164] In the formula, η is the diffraction efficiency, η max For the highest diffraction efficiency, I d For diffracted light, I t S represents transmitted light, S represents photosensitivity, E represents exposure energy, and ΔE represents the exposure energy required to achieve the highest diffraction efficiency.

[0165] After the grating is recorded, its diffraction efficiency at different angles is tested, and the refractive index modulation is obtained by fitting the Kogelnik coupled-wave theory.

[0166] Among them, the holographic exposure characteristic curves of the photopolymer-type holographic recording media provided in Application Examples 1, 6, 8, and 16 are as follows: Figure 1 As shown; the holographic exposure characteristic curve of the photopolymer holographic recording medium provided in Application Example 3 is as follows. Figure 2 As shown; by Figure 1 and Figure 2It is known that photopolymer holographic recording media, including phenyl sulfide monomers with specific structures as described in this application, have lower exposure and higher diffraction efficiency.

[0167] The specific test results are shown in Table 4.

[0168] Table 4

[0169]

[0170] As shown in Table 4, the phenyl sulfide monomers provided in this application, with a specific structural design, are used to prepare photopolymer-type holographic recording media. This is beneficial for improving the sensitivity, recording grating diffraction efficiency, and refractive index modulation of the photopolymer-type holographic recording media, while reducing its exposure. The exposure of the photopolymer-type holographic recording media including the phenyl sulfide monomers is 3.31~9.86 mJ / cm. 2 The grating diffraction efficiency is 95.6~98.84%, the sensitivity is 100.62~295.92 cm / mJ, and the refractive index modulation is 0.022~0.053.

[0171] As can be seen from the comparative application examples 1-3, for monomers that do not use the specific structure of this application, the exposure of the photopolymer holographic recording medium increases, the grating diffraction efficiency decreases significantly, the sensitivity decreases significantly, and the refractive index modulation decreases significantly.

[0172] The applicant declares that the above description is only a specific implementation of this application, but the protection scope of this application is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application fall within the protection and disclosure scope of this application.

Claims

1. A phenyl sulfide monomer, characterized in that, The phenyl sulfide monomers have the structure shown in formula G1: ； In formula G1, R1 is selected from C4 to C10 straight-chain alkyl groups, and at least two non-adjacent -CH2- groups in the C4 to C10 straight-chain alkyl groups are replaced by -S-. R2 is selected from C2~C4 alkenyl, C2~C4 alkynyl, Any one of them; A1 is selected from H or C1~C4 straight-chain or branched alkyl; The wavy line indicates the connection point.

2. The phenyl sulfide monomer according to claim 1, characterized in that, The phenyl sulfide monomers have any one of the structures shown in formula G11 and formula G12; ； R1 and R2 are each independently selected from the same range of constraints as Equation G1.

3. The phenyl sulfide monomer according to claim 1, characterized in that, In formula G1, R1 is selected from or ; In formula G1, R2 is selected from Any one of them; A1 is selected from H or methyl; The wavy line indicates the connection point.

4. The phenyl sulfide monomer according to claim 1, characterized in that, The phenyl sulfide monomers are selected from any one of the following compounds; 5. A method for preparing a phenyl sulfide monomer according to any one of claims 1 to 4, characterized in that, The preparation method includes the following steps: (1) React compound P1 with compound P2 to obtain compound P3; (2) Reaction of compound P3 with compound L1 yields a phenyl sulfide monomer having the structure shown in formula G1; Compound P1 has the structure shown in Formula I: Formula I; Compound P2 has the structure shown in Formula II: Formula II; R4 is selected from -S- or ; Compound P3 has the structure shown in Formula III: Formula III; Compound L1 has the structure shown in Formula VI: X-R2, where X is selected from halogens.

6. The preparation method according to claim 5, characterized in that, In step (1), the molar ratio of compound P1 to compound P2 is (2~3):1; The raw materials for the reaction in step (1) also include at least one of silver nitrate, potassium persulfate and solvent; based on the molar content of compound P2 being 1 mol, the molar content of silver nitrate is 2~3 mol, the molar content of potassium persulfate is 3~9 mol, and the volume of solvent is 2~10 L. The reaction in step (1) is carried out at a temperature of 40~100℃ for 1~36 h. In step (2), the molar ratio of compound L1 to compound P3 is (2~4):1; The reaction in step (2) includes: pre-reacting compound P3 with a deprotonating agent or acid-binding agent in the presence of a solvent, and then adding compound L1 to react therein.

7. A photopolymer-based holographic recording medium, characterized in that, The photopolymer-type holographic recording medium includes a writing monomer, which includes the phenyl sulfide monomers according to any one of claims 1 to 4.

8. The photopolymer-type holographic recording medium according to claim 7, characterized in that, The photopolymer-type holographic recording medium comprises the following components by weight percentage:

9. The photopolymer-type holographic recording medium according to claim 8, characterized in that, The writing monomer also includes phenyl sulfide monomers having the structure shown in Formula G2; ； In formula G2, R3 is selected from C1-C4 straight-chain or branched alkyl groups; R2 is selected from C2-C4 alkenyl, C2-C4 alkynyl, ... Any one of them; A1 is selected from H or C1~C4 straight-chain or branched alkyl; The wavy line indicates the connection point.

10. The photopolymer-type holographic recording medium according to claim 9, characterized in that, The phenyl sulfide monomer having the structure shown in Formula G2 is selected from any one of the following compounds; 11. The photopolymer-type holographic recording medium according to claim 9, characterized in that, The photopolymer-type holographic recording medium comprises 1-50% of phenyl sulfide monomers having the structure shown in Formula G1 and 1-35% of phenyl sulfide monomers having the structure shown in Formula G2.

12. A holographic optical element, characterized in that, The raw material of the holographic optical element includes the photopolymer type holographic recording medium as described in any one of claims 7 to 11.

13. An optical device, characterized in that, The optical device includes the holographic optical element as described in claim 12.

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