A high refractive monomer and its preparation method and application

Abstract

The present invention provides a high-refractive monomer and a preparation method and application thereof. A disulfide bond is constructed by a solvent chemical reaction and introduced into the monomer structure, so that the monomer structure contains both an aromatic ring and a disulfide bond. The monomer has the characteristics of low dispersion, low viscosity, high transmittance, easy synthesis by chemical methods, high repeatability, and more suitable for industrial-scale production; the composition prepared by the monomer has the characteristics of high refractive index, high mechanical strength, good resistance to bending and deformation, and high transmittance after photocuring, and can be applied to OLED, AR / MR glasses, optoelectronic devices, lens coatings, artificial lenses, optical lenses, microlenses, nanoimprinting, etc. The composition prepared by the monomer can be applied to the surface of the component by inkjet printing, spin coating, spraying, etc. and then UV cured. The monomer of the present invention can also be used to manufacture nanoimprinting glue.

Description

Technical Field

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

[0002] Photocurable monomer materials with high refractive index are increasingly being used in the field of optoelectronic devices. Their transparency after curing and high refractive index can ensure that the coating has a lower thickness and presents better brightness. The chemical structure design principle of high refractive index monomer materials is that the refractive index of monomer molecules is inversely proportional to the molar volume and proportional to the molar refractive index; at the same time, it is also necessary to consider the transparency, refractive index, dispersion, thermal stability, mechanical strength, flexibility of the monomer after curing, as well as viscosity before curing, surface tension, chemical stability and other process factors.

[0003] Typical commercial organic materials have a refractive index in the range of 1.3 to 1.6. It is an important challenge to obtain organic materials with higher refractive index and low viscosity while maintaining high optical transparency. Although the processing technology of traditional organic optical materials such as PMMA, PET, PC, CR-39 is mature and widely used, they cannot meet the use requirements of optical components due to their low refractive index and high viscosity. The optical component industry generally uses inkjet printing or spin coating to make a thin film on the surface of the device, which requires not only a high refractive index, but also high mechanical strength and high light transmittance. Therefore, the research and development of high refractive index monomers has become a hot spot and focus of research in the field of optical resins in various countries around the world. The introduction of structures with high molar refractive index and low molar volume can effectively increase the refractive index of the material, but there is currently no effective method to achieve this goal. For example, many studies have introduced sulfur atoms into monomers to increase the refractive index, and the embedding of thioethyl groups is used as a way to introduce sulfur atoms. Although this method can increase the molecular molar refractive index, it also increases the molecular molar volume and cannot achieve the comprehensive effect of increasing the refractive index.

[0004] The high-refractive monomer provided in the present application contains both an aromatic ring and a disulfide bond, has the structural characteristics of high molar refractive index and low molar volume, can effectively improve the refractive index of its material, and at the same time, has the characteristics of low dispersion, high mechanical strength, high transmittance, low viscosity, and better stability. Summary of the invention

[0005] The present invention aims to address the deficiencies of the prior art and provides a construction method for preparing a high-refractive monomer and its application. A disulfide bond is constructed by a solvent chemical reaction and introduced into the monomer structure so that the monomer structure contains both an aromatic ring and a disulfide bond. The monomer has the structural characteristics of high molar refractive index and low molar volume. After photocuring, it exhibits a higher monomer refractive index and mechanical strength, while maintaining low dispersion and viscosity, high light transmittance, good stability and resistance to bending and deformation, and excellent comprehensive performance. It can be applied to OLED, AR / MR glasses, LED, Micro-LED, optoelectronic device glasses coatings, artificial lenses, optical lenses, microlenses, nanoimprinting, etc. The composition prepared using the high-refractive monomer of the present application can be coated on the surface of the component by inkjet printing or spin coating and then UV cured to form a high-refractive functional film.

[0006] Introducing sulfur atoms in the form of disulfide bonds can truly achieve a high sulfur atom content per unit molar volume. By introducing disulfide bonds into monomers containing aromatic rings, the sulfur content per unit molar volume of monomers with aromatic rings can be significantly increased, and the advantages of both the flexible group disulfide bonds and the rigid group aromatic rings are combined. The prepared high-refractive monomer has good flexibility, good rigidity and strength, and has the characteristics of high sulfur content, low molar volume, high refractive index, low dispersion, and high light transmittance.

[0007] The present invention directly introduces disulfide bonds into monomers through solvent chemical reactions, and the constructed monomers have the characteristics of high sulfur atom content, high refractive index, low molar volume, and good stability. The disulfide bonds constructed in the monomers of the present invention are reversible covalent bonds, which can achieve reversible bond breaking and bond formation under light, heat, acid and alkaline conditions, and have a self-repairing function. The composition prepared using the high-refractive monomer of the present invention is coated on the surface of the flexible component and then UV cured to form a film. During the bending and deformation process of the flexible component, the formed cured film can improve its anti-bending and deformation performance through self-repairing.

[0008] The present invention introduces a disulfide bond and an aromatic ring into the high-refractive monomer, thereby increasing its refractive index and mechanical strength. The number of aromatic rings introduced into the high-refractive monomer molecule is 1-2 (the number of aromatic rings exceeding 3 will increase the viscosity and dispersion of the product), preferably a heteroatom-free aromatic ring represented by a benzene ring. The high-refractive monomer of the present invention has good stability and transmittance, and also has the characteristics of low viscosity and low dispersion.

[0009] The invention introduces a disulfide bond and an aromatic ring into a monomer at the same time, wherein the introduced disulfide bond has the characteristics of good flexibility, and the introduced aromatic ring has the characteristics of good rigidity, and the number of the disulfide bond and the functional group (carbon-carbon double bond, carbon-carbon triple bond, or ethylene oxide bond) is the same, and the monomer is easier to synthesize by chemical method, and the structure is stable; the invention introduces 1-2 aromatic rings into the monomer to achieve excellent stability and transparency, and also has the characteristics of low viscosity and low dispersion. The monomer of the invention has the characteristics of high refractive index, high mechanical strength, good flexibility, low dispersion, low viscosity and high light transmittance.

[0010] The preparation method of the high refractive monomer provided by the present invention uses dithiol or dithiol as a starting material, reacts with a halide under alkaline conditions to prepare a thiol or alcohol intermediate, and the thiol or alcohol group of the intermediate can react with (meth) acryloyl chloride or 3-chloro (meth) propylene to obtain a target monomer. A solvent-based chemical reaction is used to construct a disulfide bond, which is introduced into the monomer structure, has high repeatability, and is suitable for industrial-scale production.

[0011] In one aspect, the present invention provides a high-refractive monomer comprising an aromatic ring, a disulfide bond, and a photocurable functional group.

[0012] Furthermore, the number of the aromatic rings is 1 or 2; the number of the disulfide bonds is the same as the number of the photocurable functional groups, which is 1 to 6.

[0013] Furthermore, the photocurable functional group is at least one of a carbon-carbon double bond, a carbon-carbon triple bond or an ethylene oxide bond.

[0014] Furthermore, when the number of disulfide bonds and photocurable functional groups is 1, the structural formula of the high refractive monomer is as shown in Formula I:

[0015]

[0016] Wherein, the benzene ring substituent R1 is a straight-chain alkyl substituent, a branched alkyl substituent, an alkoxy substituent, an alkylthio substituent, an aryl substituent, or a halogen substituent, and the substituent position may be in the ortho position, the para position, or the meta position; t is the number of substituents, 5≥t≥0; when there are multiple substituents, the substituents may be the same or different; n is the number of methylene groups, 0≤n≤8; R2 is an alkyl substituent, an alkoxy substituent, an alkylthio substituent, or a halogen substituent, and R3 may be the same as or different from R2; X is an oxygen or sulfur atom; m is the number of ethoxy groups or ethylthio groups, 0≤m≤10; and F is a photocurable functional group.

[0017] Further, the R1 is selected from H 2y+1 C y -S-*、H 2y+1 Cy -O-*、H 2y+1 C y -*、Cl-*、Br-*、I-*、 Any one or more of H, wherein y is the number of carbon atoms in the saturated alkyl chain, 0≤y≤10.

[0018] In order to obtain a higher refractive index, the benzene ring substituent R1 is preferably (phenylthio) or (cyclopentyl dithiolate).

[0019] Further, the F is selected from Any one of, wherein R4 is a methyl group or a hydrogen atom.

[0020] Furthermore, when R1 is H, the structural formula of the high refractive monomer is any one selected from Formula I-1, Formula I-2, Formula I-3 or Formula I-4:

[0021]

[0022] When R1 is When the high refractive monomer has a structural formula selected from any one of Formula I-5, Formula I-6, Formula I-7 or Formula I-8:

[0023]

[0024] When R1 is When the high refractive monomer has a structural formula selected from any one of Formula I-9, Formula I-10, Formula I-11 or Formula I-12:

[0025]

[0026] When R1 is When the high refractive monomer has a structural formula selected from any one of Formula I-13, Formula I-14, Formula I-15 or Formula I-16:

[0027]

[0028] When R1 is When the high refractive monomer has a structural formula selected from any one of Formula I-17, Formula I-18, Formula I-19 or Formula I-20:

[0029]

[0030] Furthermore, when the number of disulfide bonds and photocurable functional groups is 2, the structural formula of the high refractive monomer is as shown in Formula II:

[0031]

[0032] Wherein, n is the number of methylene groups, 0≤n≤8; R2 is an alkyl substituent, an alkoxy substituent, an alkylthio substituent, or a halogen substituent, R3 may be the same as or different from R2; X is an oxygen or sulfur atom; m is the number of ethoxy or ethylthio groups, 0≤m≤10; F is a photocurable functional group; and A is a disubstituted aromatic group.

[0033] Further, the A is selected from wherein Z is an oxygen or sulfur atom.

[0034] When the number of disulfide bonds and photocurable functional groups is 2, the two substituents on the benzene ring can be located in the para position, ortho position or meta position according to the different selections of A. From the convenience of monomer preparation, the para position is preferred, such as When Z is S, the refractive index can be further increased.

[0035] Furthermore, when A is (para-substituted), the structural formula of the high refractive monomer is any one selected from Formula II-1, Formula II-2, Formula II-3 or Formula II-4:

[0036]

[0037] When A is When Z is a sulfur atom, the structural formula of the high refractive monomer is any one selected from Formula II-5, Formula II-6, Formula II-7 or Formula II-8:

[0038]

[0039] Furthermore, when the number of the disulfide bonds and the number of the photocurable functional groups are both 3, the structural formula of the high refractive monomer is as shown in Formula III:

[0040]

[0041] Wherein, n is the number of methylene groups, 0≤n≤8; R2 is an alkyl substituent, an alkoxy substituent, an alkylthio substituent, or a halogen substituent, and R3 may be the same as or different from R2; X is an oxygen or sulfur atom; m is the number of ethoxy or ethylthio groups, 0≤m≤10; and F is a photocurable functional group.

[0042] The monomer represented by Formula III is substituted with 1,3,5 on the benzene ring. The positions of the three substituents on the benzene ring can be substituted with 1,2,3, 1,2,4 or 1,3,5. Considering the convenience of monomer preparation, substituted with 1,3,5 is preferred.

[0043] Furthermore, the structural formula of the high refractive monomer is any one selected from Formula III-1, Formula III-2, III-3 or III-4:

[0044]

[0045] In another aspect, the present invention provides a method for preparing a high refractive monomer, the method comprising the following steps:

[0046] (1) Preparation

[0047] (2) Preparation The reaction formula is:

[0048] (3) Preparation by reaction with halides

[0049] Wherein, R1 is a straight-chain alkyl substituent, a branched alkyl substituent, an alkoxy substituent, an alkylthio substituent, an aryl substituent, or a halogen substituent; the substituent position may be at the ortho, para, or meta position of Se; t is the number of substituents, 5≥t≥0; when there are multiple substituents, the substituents may be the same or different; n is the number of methylene groups, 0≤n≤8; R2 is an alkyl substituent, an alkoxy substituent, an alkylthio substituent, or a halogen substituent, and R3 may be the same as or different from R2; X is an oxygen or sulfur atom; m is the number of ethoxy or ethylthio groups, 0≤m≤10; and F is a photocurable functional group.

[0050] Furthermore, the reaction formula of step (1) is:

[0051]

[0052] Further, the reaction formula of step (2) is:

[0053]

[0054] Further, in step (3), when m>0, the reaction formula is:

[0055]

[0056] Among them, when m=0, the reaction formula is:

[0057]

[0058] In another aspect, the present invention provides a photocurable composition, comprising the high refractive monomer as described above, and a photoinitiator.

[0059] Furthermore, the photocurable composition is a nanoimprint adhesive, which can be coated on the surface of a material by spin coating or dispensing, and then mold pressed, UV cured, and demolded to produce a semiconductor element.

[0060] On the other hand, the present invention provides the use of the photocurable composition as described above for preparing a functional film with a high refractive index, and the method for preparing the functional film with a high refractive index is: coating it on the surface of an optoelectronic device, an AR / MR eyeglass lens surface, an OLED device surface, an eyeglass lens surface, an artificial lens material surface, an optical lens or a microlens surface by one or more methods selected from the group consisting of inkjet printing, spin coating, and spraying, and then UV curing to form a functional film with a high refractive index.

[0061] All the compositions prepared from the high-refractive monomers provided by the present invention have the characteristics of high transparency, low viscosity, low dispersion, easy processing, and photocurability, and are suitable for the application of optoelectronic devices, including but not limited to OLED, AR / MR glasses, optoelectronic devices, lens coatings, artificial lenses, optical lenses, microlenses, etc. The compositions prepared from the high-refractive monomers can be coated on the surface of the device by inkjet printing or spin coating and then UV cured to form a film.

[0062] The high-refractive monomer provided by the present invention has a flexible group disulfide bond and a rigid group aromatic ring, wherein the number of the flexible group disulfide bonds is 1-6, and the number of the rigid group aromatic rings is 1-6. The combination of the flexible group disulfide bonds and the rigid group aromatic rings enables the high-refractive monomer provided by the present invention to have both good flexibility and good rigidity and strength, and at the same time has the characteristics of high sulfur content, low molar volume, high refractive index, low dispersion and high light transmittance.

[0063] The beneficial effects of the present invention are:

[0064] 1. Provide a UV-curable high-refractive monomer, which contains both a rigid aromatic ring and a flexible disulfide bond. After photocuring, the monomer exhibits good flexibility, rigidity and strength, and has the characteristics of low dispersion, low viscosity, high light transmittance, good stability and easy processing;

[0065] 2. The high refractive monomer introduces sulfur atoms via disulfide bonds, thereby having high sulfur content, high refractive index, and low molar volume, and can maximize the effect of sulfur atoms on improving the refractive index;

[0066] 3. Easy to synthesize by chemical methods, highly reproducible, and more suitable for industrial-scale production;

[0067] 4. It can be applied to optoelectronic devices including OLED, AR / MR glasses, lens coatings, artificial lenses, optical lenses, micro lenses, etc.

[0068] 5. The high-refractive composition provided by the present invention can be coated on the surface of a component by inkjet printing, spin coating, spraying, etc. and then UV-cured. It can also be prefabricated into a semi-photocured film and then prepared on the surface of the component. BRIEF DESCRIPTION OF THE DRAWINGS

[0069] Figure 1 This is a photo of monomer I-3 when it is bent;

[0070] Figure 2 This is a photo of monomer I-3 after bending. DETAILED DESCRIPTION

[0071] The present invention will be further described in detail below in conjunction with the examples. It should be pointed out that the examples described below are intended to facilitate the understanding of the present invention and do not have any limiting effect on the present invention.

[0072] The present invention provides a method for preparing a high-refractive monomer:

[0073] The preparation method of the high refractive monomer provided in the following embodiment comprises the following steps:

[0074] (1) Preparation

[0075] The reaction formula is:

[0076] (2) Preparation of dithiols with aromatic groups

[0077] The reaction formula is:

[0078] Steps (1) and (2) are mainly prepared according to the reference (Free Radical Biology and Medicine 89 (2015) 662–667). The route for preparing benzodithiol according to the reference is shown in the figure below:

[0079]

[0080] This method can be applied to the preparation of dithiols of various aromatic groups in the present invention. The corresponding dithiols can be prepared by replacing the substrate 5 in the reaction step iii. The specific corresponding relationship of the intermediate products is shown as follows:

[0081]

[0082]

[0083] (3) Dithiols of aromatic groups Preparation by reaction with halides

[0084] Using dithiol or dithiol as the starting material, a thiol or alcohol intermediate is prepared by reacting with a halide under alkaline conditions. The thiol or alcohol group of the intermediate can react with (meth)acryloyl chloride or 3-chloro(meth)propylene to obtain the target monomer.

[0085] When m>0, the reaction formula is:

[0086]

[0087] Among them, when m=0, the reaction formula is:

[0088]

[0089] Example 1 Preparation of Monomer I-1

[0090] The synthesis process of monomer (I-1): 1-allyl-2-benzyldisulfane is as follows:

[0091]

[0092] Benzyl dithiol (Compound 7) was used as a raw material. Compound 7 (50 g, 320.5 mmol) was dissolved in dry dichloromethane (500 ml) in a three-necked flask. The system was placed in an ice-water bath for cooling. Triethylamine (64.8 g, 640.5 mmol) was first added. A magnetic stirrer was placed inside the three-necked flask to stir evenly. 3-Chloropropene (26.1 g, 352.6 mmol) was injected into the dropping funnel of the branch tube. 3-Chloropropene was added dropwise under ice-bath conditions. A white precipitate was produced during the addition. After the addition was completed, the ice was removed. The system was naturally warmed to room temperature in a water bath. After the reaction was allowed to react overnight, water was added to quench the reaction. After the addition of water, the white turbidity in the system disappeared, and the aqueous layer and the dichloromethane were clearly separated. A separatory funnel was used to separate the aqueous layer and the organic layer. The aqueous layer was extracted twice with clean dichloromethane, and then all the organic solutions were combined. The organic solution was dried over anhydrous magnesium sulfate, and the solvent was removed to obtain a crude product. The product was separated by silica gel column chromatography using dichloromethane and petroleum ether as developing agents to separate the target product (32.5 g, 65%). Monomer I-1 was a colorless liquid with a refractive index of 1.615.

[0093] Example 2 Preparation of Monomer I-2

[0094] The synthesis process of monomer (I-2): SS-benzyl prop-2-ene (dithioperoxoate) is as follows:

[0095]

[0096] In a three-necked flask, compound 7 (50 g, 320.5 mmol) was dissolved in dry dichloromethane (500 ml), and the system was cooled in an ice-water bath. Triethylamine (64.8 g, 640.5 mmol) was first added, and a magnetic stirrer was placed inside the three-necked flask. Acryloyl chloride (31.7 g, 352.6 mmol) was added. The mixture was injected into the dropping funnel of the branch pipe, and acryloyl chloride was added dropwise under ice bath conditions. A white precipitate was produced during the dropping process. After the dropping was completed, the ice water bath was removed, and the system was naturally warmed to room temperature. After the reaction was allowed to proceed overnight, water was added to quench the reaction. After the addition of water, the white turbidity of the system disappeared, and the aqueous layer and dichloromethane were clearly separated. A separating funnel was used to separate the aqueous layer and the organic layer, and the aqueous layer was extracted twice with clean dichloromethane. All organic solutions were then combined, and the organic solution was dried over anhydrous magnesium sulfate. The solvent was removed to obtain a crude product, which was separated by silica gel column chromatography using dichloromethane and petroleum ether as developing agents to separate the target product (46.4 g, 69%). Monomer I-2 was a colorless liquid with a refractive index of 1.629.

[0097] Example 3 Preparation of Monomer I-3

[0098] The synthesis process of monomer (I-3): 1-allyl-2-phenyldisulfane is as follows:

[0099]

[0100] In a three-necked flask, compound 9 (50 g, 352.1 mmol) was dissolved in dry dichloromethane (500 ml), and the system was placed in an ice-water bath for cooling. Triethylamine (71.2 g, 704.2 mmol) was first added, and a magnetic stirrer was placed inside the three-necked flask. 3-Chloropropene (28.7 g, 387.3 mmol) was added. Pour into the dropping funnel of the branch pipe, add 3-chloropropylene dropwise under ice bath conditions, a white precipitate is produced during the dropping process, after the dropping is completed, remove the ice water bath, and naturally warm the system to room temperature. After the reaction is left overnight, water is added to quench the reaction. After adding water, the white turbidity of the system disappears, and the water layer and dichloromethane are clearly separated. Use a separatory funnel to separate the water layer and the organic layer, and then extract the water layer twice with clean dichloromethane, then combine all the organic solutions, dry the organic solution with anhydrous magnesium sulfate, remove the solvent, and obtain a crude product. Use silica gel column chromatography to separate, dichloromethane and petroleum ether as developing agents to separate the target product (34.6 g, 54%). Monomer I-3 appears as a colorless liquid with a refractive index of 1.625.

[0101] Example 4 Preparation of Monomer I-4

[0102] The synthesis process of monomer (I-4): SS-phenyl prop-2-ene (dithioperoxoate) is as follows:

[0103]

[0104] In a three-necked flask, compound 9 (50 g, 352.1 mmol) was dissolved in dry dichloromethane (500 ml), and the system was cooled in an ice-water bath. Triethylamine (71.2 g, 704.2 mmol) was first added, and a magnetic stirrer was placed inside the three-necked flask. Acryloyl chloride (34.9 g, 387.3 mmol) was added. The mixture was injected into the dropping funnel of the branch pipe, and acryloyl chloride was added dropwise under ice bath conditions. A white precipitate was produced during the dropping process. After the dropping was completed, the ice water bath was removed, and the system was naturally warmed to room temperature. After the reaction was allowed to proceed overnight, water was added to quench the reaction. After the addition of water, the white turbidity of the system disappeared, and the aqueous layer and dichloromethane were clearly separated. A separating funnel was used to separate the aqueous layer and the organic layer, and the aqueous layer was extracted twice with clean dichloromethane. All organic solutions were then combined, and the organic solution was dried over anhydrous magnesium sulfate. The solvent was removed to obtain a crude product. The crude product was separated by silica gel column chromatography using dichloromethane and petroleum ether as developing agents to separate the target product (42.8 g, 62%). Monomer I-4 was a colorless liquid with a refractive index of 1.605.

[0105] Example 5 Preparation of Monomer I-5

[0106] The synthesis process of monomer (I-5): 1-allyl-2-(4-(phenylthio)benzyl)disulfane is as follows:

[0107]

[0108] In a three-necked flask, compound 11 (50 g, 189.4 mmol) was dissolved in dry dichloromethane (500 ml), and the system was cooled in an ice-water bath. Triethylamine (38.3 g, 378.8 mmol) was first added, and a magnetic stirrer was placed inside the three-necked flask. 3-Chloropropene (15.4 g, 208.3 mmol) was added. Pour into the dropping funnel of the branch pipe, add 3-chloropropylene dropwise under ice bath conditions, a white precipitate is produced during the dropping process, after the dropping is completed, remove the ice water bath, and naturally warm the system to room temperature. After the reaction is left overnight, water is added to quench the reaction. After adding water, the white turbidity of the system disappears, and the water layer and dichloromethane are clearly separated. Use a separatory funnel to separate the water layer and the organic layer, and then extract the water layer twice with clean dichloromethane, then combine all the organic solutions, dry the organic solution with anhydrous magnesium sulfate, remove the solvent, and obtain a crude product. Use silica gel column chromatography to separate, dichloromethane and petroleum ether as developing agents to separate the target product (38.0 g, 66%). Monomer I-5 appears as a colorless liquid with a refractive index of 1.655.

[0109] Example 6 Preparation of Monomer I-6

[0110] The synthesis process of monomer (I-6): SS-(4-(phenylthio)benzyl)prop-2-ene (dithioperoxoate) is as follows:

[0111]

[0112] In a three-necked flask, compound 11 (50 g, 189.4 mmol) was dissolved in dry dichloromethane (500 ml), and the system was cooled in an ice-water bath. Triethylamine (38.3 g, 378.8 mmol) was first added, and a magnetic stirrer was placed inside the three-necked flask. Acryloyl chloride (18.7 g, 208.3 mmol) was added. The mixture was injected into the dropping funnel of the branch pipe, and acryloyl chloride was added dropwise under ice bath conditions. A white precipitate was produced during the dropping process. After the dropping was completed, the ice water bath was removed, and the system was naturally warmed to room temperature. After the reaction was allowed to proceed overnight, water was added to quench the reaction. After the addition of water, the white turbidity of the system disappeared, and the aqueous layer and dichloromethane were clearly separated. A separating funnel was used to separate the aqueous layer and the organic layer, and the aqueous layer was extracted twice with clean dichloromethane. All organic solutions were then combined, and the organic solution was dried over anhydrous magnesium sulfate. The solvent was removed to obtain a crude product, which was separated by silica gel column chromatography using dichloromethane and petroleum ether as developing agents to separate the target product (39.2 g, 65%). Monomer I-6 was a colorless liquid with a refractive index of 1.660.

[0113] Example 7 Preparation of Monomer I-7

[0114] The synthesis process of monomer (I-7): 1-allyl-2-(4-(phenylthio)phenyl)disulfane is as follows:

[0115]

[0116] In a three-necked flask, compound 13 (50.0 g, 200.0 mmol) was dissolved in dry dichloromethane (500 ml), and the system was placed in an ice-water bath for cooling. Triethylamine (40.4 g, 400.0 mmol) was first added, and a magnetic stirrer was placed inside the three-necked flask. 3-Chloropropene (16.3 g, 220.0 mmol) was added. Pour into the dropping funnel of the branch pipe, add 3-chloropropylene dropwise under ice bath conditions, a white precipitate is produced during the dropping process, after the dropping is completed, remove the ice water bath, and naturally return the system to room temperature. After the reaction is left overnight, water is added to quench the reaction. After adding water, the white turbidity of the system disappears, and the water layer and dichloromethane are clearly separated. Use a separatory funnel to separate the water layer and the organic layer, and then extract the water layer twice with clean dichloromethane, then combine all the organic solutions, dry the organic solution with anhydrous magnesium sulfate, remove the solvent, and obtain a crude product. Use silica gel column chromatography to separate, dichloromethane and petroleum ether as developing agents to separate the target product (32.5 g, 56%). Monomer I-7 appears as a colorless liquid with a refractive index of 1.665.

[0117] Example 8 Preparation of Monomer I-8

[0118] The synthesis process of monomer (I-8): SS-(4-(phenylthio)phenyl)prop-2-ene(dithioperoxoate) is as follows:

[0119]

[0120] In a three-necked flask, compound 13 (50 g, 200.0 mmol) was dissolved in dry dichloromethane (500 ml), and the system was placed in an ice-water bath for cooling. Triethylamine (40.4 g, 400.0 mmol) was first added, and a magnetic stirrer was placed inside the three-necked flask. Acryloyl chloride (19.8 g, 220.0 mmol) was added. The mixture was injected into the dropping funnel of the branch pipe, and acryloyl chloride was added dropwise under ice bath conditions. A white precipitate was produced during the dropping process. After the dropping was completed, the ice water bath was removed, and the system was naturally warmed to room temperature. After the reaction was allowed to proceed overnight, water was added to quench the reaction. After the addition of water, the white turbidity of the system disappeared, and the aqueous layer and dichloromethane were clearly separated. A separating funnel was used to separate the aqueous layer and the organic layer, and the aqueous layer was extracted twice with clean dichloromethane. All organic solutions were then combined, and the organic solution was dried over anhydrous magnesium sulfate. The solvent was removed to obtain a crude product, which was separated by silica gel column chromatography using dichloromethane and petroleum ether as developing agents to separate the target product (31.6 g, 52%). Monomer I-8 was a colorless liquid with a refractive index of 1.671.

[0121] Example 9 Preparation of Monomer I-9

[0122] The synthesis process of monomer (I-9): 1-allyl-2-(4-phenoxybenzyl)disulfane is as follows:

[0123]

[0124] In a three-necked flask, compound 15 (50.0 g, 201.6 mmol) was dissolved in dry dichloromethane (500 ml), and the system was placed in an ice-water bath for cooling. Triethylamine (40.8 g, 403.2 mmol) was first added, and a magnetic stirrer was placed inside the three-necked flask. 3-Chloropropene (16.4 g, 221.8 mmol) was added. Pour into the dropping funnel of the branch pipe, add 3-chloropropylene dropwise under ice bath conditions, a white precipitate is produced during the dropping process, after the dropping is completed, remove the ice water bath, and naturally warm the system to room temperature. After the reaction is left overnight, water is added to quench the reaction. After adding water, the white turbidity of the system disappears, and the water layer and dichloromethane are clearly separated. Use a separatory funnel to separate the water layer and the organic layer, and then extract the water layer twice with clean dichloromethane, then combine all the organic solutions, dry the organic solution with anhydrous magnesium sulfate, remove the solvent, and obtain a crude product. Use silica gel column chromatography to separate, dichloromethane and petroleum ether as developing agents to separate the target product (39.5 g, 68%). Monomer I-9 appears as a colorless liquid with a refractive index of 1.621.

[0125] Example 10 Preparation of Monomer I-10

[0126] The synthesis process of monomer (I-10): SS-(4-phenoxybenzyl)prop-2-ene (dithioperoxoate) is as follows:

[0127]

[0128] In a three-necked flask, compound 15 (50 g, 201.6 mmol) was dissolved in dry dichloromethane (500 ml), and the system was cooled in an ice-water bath. Triethylamine (40.4 g, 403.2 mmol) was first added, and a magnetic stirrer was placed inside the three-necked flask. Acryloyl chloride (20.0 g, 221.8 mmol) was added. The mixture was injected into the dropping funnel of the branch pipe, and acryloyl chloride was added dropwise under ice bath conditions. A white precipitate was produced during the dropping process. After the dropping was completed, the ice water bath was removed, and the system was naturally warmed to room temperature. After the reaction was allowed to proceed overnight, water was added to quench the reaction. After the addition of water, the white turbidity of the system disappeared, and the aqueous layer and dichloromethane were clearly separated. A separating funnel was used to separate the aqueous layer and the organic layer, and the aqueous layer was extracted twice with clean dichloromethane. All organic solutions were then combined, and the organic solution was dried over anhydrous magnesium sulfate. The solvent was removed to obtain a crude product, which was separated by silica gel column chromatography using dichloromethane and petroleum ether as developing agents to separate the target product (39.6 g, 65%). Monomer I-10 was a colorless liquid with a refractive index of 1.625.

[0129] Example 11 Preparation of Monomer I-11

[0130] The synthesis process of monomer (I-11): 1-allyl-2-(4-phenoxyphenyl)disulfane is as follows:

[0131]

[0132] In a three-necked flask, compound 17 (50.0 g, 213.7 mmol) was dissolved in dry dichloromethane (500 ml), and the system was placed in an ice-water bath for cooling. Triethylamine (43.2 g, 427.4 mmol) was first added, and a magnetic stirrer was placed inside the three-necked flask. 3-Chloropropene (17.4 g, 235.1 mmol) was added. Pour into the dropping funnel of the branch pipe, add 3-chloropropylene dropwise under ice bath conditions, a white precipitate is produced during the dropping process, after the dropping is completed, remove the ice water bath, and naturally warm the system to room temperature. After the reaction is left overnight, water is added to quench the reaction. After adding water, the white turbidity of the system disappears, and the water layer and dichloromethane are clearly separated. Use a separatory funnel to separate the water layer and the organic layer, and then extract the water layer twice with clean dichloromethane, then combine all the organic solutions, dry the organic solution with anhydrous magnesium sulfate, remove the solvent, and obtain a crude product. Use silica gel column chromatography to separate, dichloromethane and petroleum ether as developing agents to separate the target product (32.8 g, 56%). Monomer I-11 is a colorless liquid with a refractive index of 1.634.

[0133] Example 12 Preparation of Monomer I-12

[0134] The synthesis process of monomer (I-12): SS-(4-phenoxyphenyl)prop-2-ene (dithioperoxoate) is as follows:

[0135]

[0136] In a three-necked flask, compound 17 (50.0 g, 213.7 mmol) was dissolved in dry dichloromethane (500 ml), and the system was placed in an ice-water bath for cooling. Triethylamine (43.2 g, 427.4 mmol) was first added, and a magnetic stirrer was placed inside the three-necked flask. Acryloyl chloride (21.2 g, 235.1 mmol) was added. The mixture was injected into the dropping funnel of the branch pipe, and acryloyl chloride was added dropwise under ice bath conditions. A white precipitate was produced during the addition process. After the addition was completed, the ice water bath was removed, and the system was naturally warmed to room temperature. After the reaction was allowed to proceed overnight, water was added to quench the reaction. After the addition of water, the white turbidity of the system disappeared, and the aqueous layer and dichloromethane were clearly separated. A separating funnel was used to separate the aqueous layer and the organic layer, and the aqueous layer was extracted twice with clean dichloromethane. All organic solutions were then combined, and the organic solution was dried over anhydrous magnesium sulfate. The solvent was removed to obtain a crude product. The crude product was separated by silica gel column chromatography using dichloromethane and petroleum ether as developing agents to separate the target product (35.7 g, 58%). Monomer I-12 was a colorless liquid with a refractive index of 1.639.

[0137] Example 13 Preparation of Monomer I-13

[0138] The synthesis process of monomer (I-13): 1-([1,1'-biphenyl]-4-ylmethyl)-2-allyldisulfane is as follows:

[0139]

[0140] In a three-necked flask, compound 19 (50.0 g, 215.5 mmol) was dissolved in dry dichloromethane (500 ml), and the system was placed in an ice-water bath for cooling. Triethylamine (43.6 g, 431.0 mmol) was first added, and a magnetic stirrer was placed inside the three-necked flask. 3-Chloropropene (17.5 g, 237.0 mmol) was added. Pour into the dropping funnel of the branch pipe, add 3-chloropropylene dropwise under ice bath conditions, a white precipitate is produced during the dropping process, after the dropping is completed, remove the ice water bath, and naturally warm the system to room temperature. After the reaction is left overnight, water is added to quench the reaction. After adding water, the white turbidity of the system disappears, and the water layer and dichloromethane are clearly separated. Use a separatory funnel to separate the water layer and the organic layer, and then extract the water layer twice with clean dichloromethane, then combine all the organic solutions, dry the organic solution with anhydrous magnesium sulfate, remove the solvent, and obtain a crude product. Use silica gel column chromatography to separate, dichloromethane and petroleum ether as developing agents to separate the target product (39.3 g, 67%). Monomer I-13 appears as a colorless liquid with a refractive index of 1.644.

[0141] Example 14 Preparation of Monomer I-14

[0142] The synthesis process of monomer (I-14): SS-([1,1'-biphenyl]-4-ylmethyl)prop-2-ene (dithioperoxoate) is as follows:

[0143]

[0144] In a three-necked flask, compound 19 (50.0 g, 215.5 mmol) was dissolved in dry dichloromethane (500 ml), and the system was placed in an ice-water bath for cooling. Triethylamine (43.6 g, 431.0 mmol) was first added, and a magnetic stirrer was placed inside the three-necked flask. Acryloyl chloride (21.3 g, 237.0 mmol) was added. The mixture was injected into the dropping funnel of the branch pipe, and acryloyl chloride was added dropwise under ice bath conditions. A white precipitate was produced during the addition process. After the addition was completed, the ice water bath was removed, and the system was naturally warmed to room temperature. After the reaction was allowed to proceed overnight, water was added to quench the reaction. After the addition of water, the white turbidity of the system disappeared, and the aqueous layer and dichloromethane were clearly separated. A separating funnel was used to separate the aqueous layer and the organic layer, and the aqueous layer was extracted twice with clean dichloromethane. All organic solutions were then combined, and the organic solution was dried over anhydrous magnesium sulfate. The solvent was removed to obtain a crude product. The crude product was separated by silica gel column chromatography using dichloromethane and petroleum ether as developing agents to separate the target product (40.4 g, 69%). Monomer I-14 was a colorless liquid with a refractive index of 1.646.

[0145] Example 15 Preparation of Monomer I-15

[0146] The synthesis process of monomer (I-15): 1-([1,1'-biphenyl]-4-yl)-2-allyldisulfane is as follows:

[0147]

[0148] In a three-necked flask, compound 21 (50.0 g, 229.4 mmol) was dissolved in dry dichloromethane (500 ml), and the system was placed in an ice-water bath for cooling. Triethylamine (46.4 g, 458.7 mmol) was first added, and a magnetic stirrer was placed inside the three-necked flask. 3-Chloropropene (18.7 g, 252.3 mmol) was added. Pour into the dropping funnel of the branch pipe, add 3-chloropropylene dropwise under ice bath conditions, a white precipitate is produced during the dropping process, after the dropping is completed, remove the ice water bath, and naturally warm the system to room temperature. After the reaction is left overnight, water is added to quench the reaction. After adding water, the white turbidity of the system disappears, and the water layer and dichloromethane are clearly separated. Use a separatory funnel to separate the water layer and the organic layer, and then extract the water layer twice with clean dichloromethane, then combine all the organic solutions, dry the organic solution with anhydrous magnesium sulfate, and remove the solvent to obtain a crude product. Use silica gel column chromatography to separate, dichloromethane and petroleum ether as developing agents to separate the target product (30.8 g, 52%). Monomer I-15 is a colorless liquid with a refractive index of 1.656.

[0149] Example 16 Preparation of Monomer I-16

[0150] The synthesis process of monomer (I-16): SS-([1,1'-biphenyl]-4-yl)prop-2-ene (dithioperoxoate) is as follows:

[0151]

[0152] In a three-necked flask, compound 21 (50.0 g, 229.4 mmol) was dissolved in dry dichloromethane (500 ml), and the system was placed in an ice-water bath for cooling. Triethylamine (46.4 g, 458.7 mmol) was first added, and a magnetic stirrer was placed inside the three-necked flask. Acryloyl chloride (22.7 g, 252.3 mmol) was added. The mixture was injected into the dropping funnel of the branch pipe, and acryloyl chloride was added dropwise under ice bath conditions. A white precipitate was produced during the addition process. After the addition was completed, the ice water bath was removed, and the system was naturally warmed to room temperature. After the reaction was allowed to proceed overnight, water was added to quench the reaction. After the addition of water, the white turbidity of the system disappeared, and the aqueous layer and dichloromethane were clearly separated. A separating funnel was used to separate the aqueous layer and the organic layer, and the aqueous layer was extracted twice with clean dichloromethane. All organic solutions were then combined, and the organic solution was dried over anhydrous magnesium sulfate. The solvent was removed to obtain a crude product, which was separated by silica gel column chromatography using dichloromethane and petroleum ether as developing agents to separate the target product (34.3 g, 55%). Monomer I-16 was a colorless liquid with a refractive index of 1.656.

[0153] Example 17 Preparation of Monomer I-17

[0154] The synthesis process of monomer (I-17): 2-(4-((allyldisulfaneyl)methyl)phenyl)-1,3-dithiolane is as follows:

[0155]

[0156] In a three-necked flask, compound 23 (50.0 g, 192.3 mmol) was dissolved in dry dichloromethane (500 ml), and the system was placed in an ice-water bath for cooling. Triethylamine (38.9 g, 384.6 mmol) was first added, and a magnetic stirrer was placed inside the three-necked flask. 3-Chloropropene (15.7 g, 211.5 mmol) was added. Pour into the dropping funnel of the branch pipe, add 3-chloropropylene dropwise under ice bath conditions, a white precipitate is produced during the dropping process, after the dropping is completed, remove the ice water bath, and naturally warm the system to room temperature. After the reaction is left overnight, water is added to quench the reaction. After adding water, the white turbidity of the system disappears, and the water layer and dichloromethane are clearly separated. Use a separatory funnel to separate the water layer and the organic layer, and then extract the water layer twice with clean dichloromethane, then combine all the organic solutions, dry the organic solution with anhydrous magnesium sulfate, and remove the solvent to obtain a crude product. Use silica gel column chromatography to separate, dichloromethane and petroleum ether as developing agents to separate the target product (38.7 g, 67%). Monomer I-17 appears as a colorless liquid with a refractive index of 1.685.

[0157] Example 18 Preparation of Monomer I-18

[0158] The synthesis process of monomer (I-18): SS-(4-(1,3-dithiolan-2-yl)benzyl)prop-2-ene(dithioperoxoate) is as follows:

[0159]

[0160] In a three-necked flask, compound 23 (50.0 g, 192.3 mmol) was dissolved in dry dichloromethane (500 ml), and the system was cooled in an ice-water bath. Triethylamine (38.9 g, 384.6 mmol) was first added, and a magnetic stirrer was placed inside the three-necked flask. Acryloyl chloride (19.0 g, 211.5 mmol) was added. The mixture was injected into the dropping funnel of the branch pipe, and acryloyl chloride was added dropwise under ice bath conditions. A white precipitate was produced during the addition process. After the addition was completed, the ice water bath was removed, and the system was naturally warmed to room temperature. After the reaction was allowed to proceed overnight, water was added to quench the reaction. After the addition of water, the white turbidity of the system disappeared, and the aqueous layer and dichloromethane were clearly separated. A separating funnel was used to separate the aqueous layer and the organic layer, and the aqueous layer was extracted twice with clean dichloromethane. All organic solutions were then combined, and the organic solution was dried over anhydrous magnesium sulfate. The solvent was removed to obtain a crude product. The crude product was separated by silica gel column chromatography using dichloromethane and petroleum ether as developing agents to separate the target product (41.7 g, 69%). Monomer I-18 was a colorless liquid with a refractive index of 1.686.

[0161] Example 19 Preparation of Monomer I-19

[0162] The synthesis process of monomer (I-19): 2-(4-(allyldisulfaneyl)phenyl)-1,3-dithiolane is as follows:

[0163]

[0164] In a three-necked flask, compound 25 (50.0 g, 203.3 mmol) was dissolved in dry dichloromethane (500 ml), and the system was placed in an ice-water bath for cooling. Triethylamine (41.1 g, 406.5 mmol) was first added, and a magnetic stirrer was placed inside the three-necked flask. 3-Chloropropene (16.5 g, 223.6 mmol) was added. Pour into the dropping funnel of the branch pipe, add 3-chloropropylene dropwise under ice bath conditions, a white precipitate is produced during the dropping process, after the dropping is completed, remove the ice water bath, and naturally warm the system to room temperature. After the reaction is left overnight, water is added to quench the reaction. After adding water, the white turbidity of the system disappears, and the water layer and dichloromethane are clearly separated. Use a separatory funnel to separate the water layer and the organic layer, and then extract the water layer twice with clean dichloromethane, then combine all the organic solutions, dry the organic solution with anhydrous magnesium sulfate, and remove the solvent to obtain a crude product. Use silica gel column chromatography to separate, dichloromethane and petroleum ether as developing agents to separate the target product (30.8 g, 53%). Monomer I-19 appears as a colorless liquid with a refractive index of 1.695.

[0165] Example 20 Preparation of Monomer I-20

[0166] The synthesis process of monomer (I-20): SS-(4-(1,3-dithiolan-2-yl)phenyl)prop-2-ene(dithioperoxoate) is as follows:

[0167]

[0168] In a three-necked flask, compound 23 (50.0 g, 203.3 mmol) was dissolved in dry dichloromethane (500 ml), and the system was cooled in an ice-water bath. Triethylamine (41.1 g, 406.5 mmol) was first added, and a magnetic stirrer was placed inside the three-necked flask. Acryloyl chloride (19.0 g, 223.6 mmol) was added. The mixture was injected into the dropping funnel of the branch pipe, and acryloyl chloride was added dropwise under ice bath conditions. A white precipitate was produced during the dropping process. After the dropping was completed, the ice water bath was removed, and the system was naturally warmed to room temperature. After the reaction was allowed to proceed overnight, water was added to quench the reaction. After the addition of water, the white turbidity of the system disappeared, and the aqueous layer and dichloromethane were clearly separated. A separating funnel was used to separate the aqueous layer and the organic layer, and the aqueous layer was extracted twice with clean dichloromethane. All organic solutions were then combined, and the organic solution was dried over anhydrous magnesium sulfate. The solvent was removed to obtain a crude product, which was separated by silica gel column chromatography using dichloromethane and petroleum ether as developing agents to separate the target product (30.5 g, 50%). Monomer I-20 was a colorless liquid with a refractive index of 1.696.

[0169] Example 21 Preparation of Monomer II-1

[0170] The synthesis process of monomer (II-1): 1,4-bis((allyldisulfaneyl)methyl)benzene is as follows:

[0171]

[0172] In a three-necked flask, compound 26 (50.0 g, 213.7 mmol) was dissolved in dry dichloromethane (500 ml). The system was cooled in an ice-water bath. Triethylamine (86.4 g, 854.8 mmol) was first added. A magnetic stirrer was placed inside the three-necked flask. 3-Chloropropene (34.1 g, 448.8 mmol) was injected into the dropping funnel of the branch pipe, and acryloyl chloride was added dropwise under ice bath condition. White precipitate was produced during the dropping process. After the dropping was completed, the ice water bath was removed, and the system was naturally warmed to room temperature. After the reaction was allowed to proceed overnight, water was added to quench the reaction. After the addition of water, the white turbidity of the system disappeared, and the aqueous layer and dichloromethane were clearly separated. A separating funnel was used to separate the aqueous layer and the organic layer, and the aqueous layer was extracted twice with clean dichloromethane. All organic solutions were then combined, and the organic solution was dried over anhydrous magnesium sulfate, and the solvent was removed to obtain a crude product. The crude product was separated by silica gel column chromatography using dichloromethane and petroleum ether as developing agents to separate the target product (34.9 g, 52%). Monomer II-1 was a colorless liquid with a refractive index of 1.636.

[0173] Example 22 Preparation of Monomer II-8

[0174] The synthesis process of monomer (II-8): 1,4-bis((allyldisulfaneyl)methyl)benzene is as follows:

[0175]

[0176] In a three-necked flask, compound 27 (50.0 g, 159.3 mmol) was dissolved in dry dichloromethane (500 ml), and the system was cooled in an ice-water bath. Triethylamine (64.4 g, 637.1 mmol) was first added, and a magnetic stirrer was placed inside the three-necked flask. Acryloyl chloride (30.1 g, 334.5 mmol) was injected into the dropping funnel of the branch pipe, and acryloyl chloride was added dropwise under ice bath condition. White precipitate was produced during the dropping process. After the dropping was completed, the ice water bath was removed, and the system was naturally warmed to room temperature. After the reaction was allowed to proceed overnight, water was added to quench the reaction. After the addition of water, the white turbidity of the system disappeared, and the aqueous layer and dichloromethane were clearly separated. A separating funnel was used to separate the aqueous layer and the organic layer, and the aqueous layer was extracted twice with clean dichloromethane. All organic solutions were then combined, and the organic solution was dried over anhydrous magnesium sulfate, and the solvent was removed to obtain a crude product. The crude product was separated by silica gel column chromatography using dichloromethane and petroleum ether as developing agents to separate the target product (32.3 g, 48%). Monomer II-8 was a colorless liquid with a refractive index of 1.698.

[0177] Example 23 Preparation of Monomer III-1

[0178] The synthesis process of monomer (III-1): 1,3,5-tris((allyldisulfaneyl)methyl)benzene is as follows:

[0179]

[0180] In a three-necked flask, compound 28 (50.0 g, 160.3 mmol) was dissolved in dry dichloromethane (500 ml). The system was cooled in an ice-water bath. Triethylamine (97.2 g, 961.5 mmol) was first added. A magnetic stirrer was placed inside the three-necked flask. 3-Chloropropene (37.8 g, 496.9 mmol) was injected into the dropping funnel of the branch pipe, and acryloyl chloride was added dropwise under ice bath condition. White precipitate was produced during the dropping process. After the dropping was completed, the ice water bath was removed, and the system was naturally warmed to room temperature. After the reaction was allowed to proceed overnight, water was added to quench the reaction. After the addition of water, the white turbidity of the system disappeared, and the aqueous layer and dichloromethane were clearly separated. A separating funnel was used to separate the aqueous layer and the organic layer, and the aqueous layer was extracted twice with clean dichloromethane. All organic solutions were then combined, and the organic solution was dried over anhydrous magnesium sulfate, and the solvent was removed to obtain a crude product. The crude product was separated by silica gel column chromatography using dichloromethane and petroleum ether as developing agents to separate the target product (36.7 g, 53%). Monomer III-1 was a colorless liquid with a refractive index of 1.667.

[0181] Comparative Example 1 Preparation of a Monomer Containing a Benzene Ring and Sulfur but Without a Disulfide Bond

[0182] This example refers to patent EP0382477 to prepare a monomer containing both a benzene ring and sulfur, and its structural formula is as follows:

[0183]

[0184] Comparative Example 2 Preparation of a Monomer Containing Two Benzene Rings and Sulfur but No Disulfide Bond

[0185] This example refers to patent EP0382477 to prepare a monomer containing two benzene rings and sulfur, and its structural formula is as follows:

[0186]

[0187] Detection and analysis

[0188] In this embodiment, the monomers prepared in Examples 1 to 23 and Comparative Examples 1-2 were subjected to comprehensive performance testing. By adding a photoinitiator TPO, the monomers were photocured at a wavelength of 390 nm to test the molecular weight, sulfur content, refractive index, Abbe index, viscosity, transparency, tensile strength, shear strength and stability. The viscosity was tested before photocuring. The refractive index was tested by an Abbe refractometer. The Abbe index was tested by a dispersion analyzer. The viscosity was tested by a rotary viscometer. The transmittance was tested by inkjet printing. The thickness of the photocured film was 10 μm. , and the transmittance is tested at a wavelength of 475nm; the mechanical strength test method is to perform tensile strength test using a tensile testing machine; the bending and deformation resistance test method is to bend it 20 times in a row and then check the creases after recovery. If the creases are very slight or there are no creases, it proves that it has very good bending and deformation resistance. If the creases are obvious or it is broken, it proves that the bending and deformation resistance is poor; the stability test method is to place the sample solution in a 38℃ constant temperature box for six months and then solidify it, and compare whether there is any difference between the film layer after the stability test and the newly prepared sample solution are solidified. The test results are shown in Table 1.

[0189] Table 1. Comparison of performance of different monomers

[0190]

[0191]

[0192] As can be seen from Table 1, compared with Comparative Examples 1 and 2, the monomers containing both a benzene ring and a disulfide bond provided by the present invention (Examples 1 to 23) not only have a higher refractive index (higher than 1.6, with a significant difference from Comparative Examples 1 and 2, p < 0.01), but also have better mechanical properties, better anti-bending and deformation properties (such as Figure 1 This is a photo of monomer I-3 when it is bent. Figure 2 This is a photo of monomer I-3 after bending. Figure 2It can be seen that monomer 1-3 can be completely restored after bending without any creases), has better stability, and is easier to process. It can be seen that the monomer provided by the present invention that contains both a benzene ring and a disulfide bond gives full play to the coordination effect of the flexible disulfide bond and the rigid aromatic ring, combines the advantages of both, and has more superior comprehensive performance.

[0193] Although the monomers prepared in Comparative Examples 1 and 2 also contain sulfur and benzene rings, their sulfur content is relatively low, their refractive index is relatively low, and they do not have self-repairing capabilities. Once creases are produced, they are difficult to recover.

[0194] Comparative Examples 1 to 23 show that when the number of disulfide bonds and photocurable functional groups is 3, the prepared monomer has a higher refractive index and better mechanical strength, but the viscosity is also higher. The reason is that the molecular weight increases and the intermolecular interaction also increases. The second is the case where the number of disulfide bonds and photocurable functional groups is 2. The reason may be that the number of disulfide bonds is larger, the sulfur content is increased, and the structure is more stable and easy to process. When the number of disulfide bonds and photocurable functional groups is 2 or 3, the mechanical strength is higher and the refractive index is also higher than when the number of disulfide bonds and photocurable functional groups is 1. Among them, the monomer III-1 has the highest refractive index and the highest mechanical strength. Its dispersion is also lower and the viscosity is appropriate.

[0195] By comparing Examples 1 to 20, it can be seen that when the number of disulfide bonds and photocurable functional groups is 1, monomers I-5 to I-8 and I-17 to I-20 have relatively higher refractive index, lower dispersion and lower viscosity (Examples 13 to 16 have very high viscosity because of two consecutive benzene rings, and can be used after dilution or are suitable for some occasions requiring high viscosity, such as nanoimprint glue), and can still maintain good mechanical strength and better comprehensive performance. The reason may also be that the disulfide bond is added to the benzene ring substituent, which increases the sulfur content in the molar volume, and has a high molar refractive index and a low molar volume.

[0196] This embodiment also adopts a method similar to that of Examples 1 to 23 to prepare a high-refractive monomer having 4 to 6 disulfide bonds and photocurable functional groups. The results show that the high-refractive monomer having 4 to 6 disulfide bonds and photocurable functional groups also has the structural characteristics of high molar refractive index and low molar volume, and has a higher refractive index. At the same time, it has the characteristics of low dispersion, high mechanical strength, high light transmittance, low viscosity, and better stability.

[0197] Although the present invention is disclosed as above, the present invention is not limited thereto. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the scope defined by the claims.

Claims

1. A compound, characterized in that The structural formula is as follows:

2. A high refractive monomer, characterized in that: Its structural formula is as follows:

3. A photocurable composition, characterized in that It comprises the high refractive monomer as claimed in claim 2 and a photoinitiator.

4. The photocurable composition according to claim 3, characterized in that The photocurable composition is a nano-imprint adhesive, which can be coated on the surface of a material by spin coating or dispensing, and then mold pressed, UV cured, and demolded to produce a semiconductor element.

5. Use of the photocurable composition according to claim 3 for preparing a functional film having a high refractive index, characterized in that: The functional film is prepared by coating the film on the surface of an optoelectronic device, an AR / MR eyeglass lens, an OLED device, an eyeglass lens, an artificial lens material, an optical lens or a microlens by one or more of inkjet printing, spin coating and spraying, and then UV curing the film.

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