Compound, preparation method of compound, resin material and application of resin material

Abstract

The invention discloses a compound and a preparation method thereof as well as a resin material and application thereof, the compound provided by the invention mainly comprises two structural units, namely phosphate and thiophenyl or phenoxy or phenylamino, has high refractive index, high Abbe number and good light permeability, and is beneficial to a single bond which takes phosphorus as a center and can rotate freely, so that the compound has high refractive index, high Abbe number and good light permeability. The structural characteristics endow the material with good flexibility and toughness, so that the material can deform under external force and is not easy to break, and the material has good mechanical properties.

Description

Technical Field

[0001] The present application relates to the technical field of optical materials, and in particular to a compound and a preparation method thereof, a resin material and an application thereof. Background Art

[0002] Optical materials are mainly divided into two categories: glass and resin, and are widely used in many fields such as display, lens, sensor, etc. Among them, optical resin materials are gaining more and more attention in the field of optical materials.

[0003] For example, high refractive index modified polyphenylene sulfide material, but this material is very brittle and is not suitable for direct application in the optical field. Summary of the invention

[0004] In view of this, the present application proposes a compound and a preparation method thereof, a resin material and an application thereof.

[0005] The first aspect of the present application provides a compound having the following general formula:

[0006]

[0007] Among them, X is a sixth main group element;

[0008] R1 is -O-, -S- or -NH-;

[0009] R2 is a benzene ring group, a phenylthioether group or a thioether group;

[0010] R3, R4, R5 and R6 are each selected from one of a hydrogen atom, a thioether group, an ether group, a mercapto group and a phenolic hydroxyl group;

[0011] n and m are integers, 0≤n≤5, 1≤m≤10.

[0012] In some embodiments, X is any substituent selected from -O-, -S-, or -Se-.

[0013] In some embodiments, the compound has the following structural formula:

[0014] or,

[0015] or,

[0016] or,

[0017] or,

[0018] or,

[0019] or,

[0020]

[0021] A second aspect of the present application provides a resin material comprising the above-mentioned compound.

[0022] A third aspect of the present application provides an application of a resin material in optical waveguide technology.

[0023] The fourth aspect of the present application provides a method for preparing a compound, the preparation method comprising:

[0024] providing a first monomer and a second monomer;

[0025] The first monomer and the second monomer are mixed and subjected to a polymerization reaction to obtain the compound;

[0026] Wherein, the general formula of the first monomer is as follows:

[0027]

[0028] Wherein, Y is an amino group, a hydroxyl group or a thiol group, and n is an integer, 0≤n≤5;

[0029] The general formula of the second monomer is as follows:

[0030]

[0031] Among them, R1 is a halogen atom, and R2 is a benzene ring group, a phenyl sulfide group or a sulfide group.

[0032] In some embodiments, R7 is a chlorine, bromine or iodine atom.

[0033] In some embodiments, the first monomer is selected from at least one of 4,4-dihydroxydiphenyl sulfide, 1,4-phenyldithiol, 4,4'-diaminodiphenyl sulfide, and 4,4'-diamino(2,2'-methylthio)diphenyl sulfide.

[0034] In some embodiments, the second monomer is selected from at least one of phenylthiophosphoryl dichloride and phenylthiophosphoryl dichloride.

[0035] In some embodiments, the mixing of the first monomer and the second monomer and performing a polymerization reaction to obtain the compound includes: mixing the first monomer, the second monomer, a catalyst, and a solvent and performing a polymerization reaction to obtain the compound.

[0036] In some embodiments, the catalyst is selected from at least one of triethylamine, 1-methylimidazole, anhydrous potassium carbonate, and potassium iodide.

[0037] In some embodiments, the solvent is at least one of dichloromethane and acetone.

[0038] In some embodiments, the first monomer, the second monomer, the catalyst and the solvent are mixed and polymerized to obtain the compound, including:

[0039] The first monomer, the second monomer, a catalyst and a solvent are mixed and subjected to a polymerization reaction to obtain a reaction mixture including the compound;

[0040] The reaction mixture is stirred and the solvent is removed to obtain a viscous substance;

[0041] The viscous object is precipitated, washed and then vacuum dried to obtain the compound.

[0042] In some embodiments, the viscous object is precipitated and then washed with methanol or ethanol; and / or, the viscous object is precipitated, washed and then dried in a vacuum oven, the temperature is set at 70° C.-90° C., and the vacuum drying is performed for 10 hours to 15 hours.

[0043] It can be seen from the above technical scheme that the compound proposed in the present application mainly comprises two structural units, namely phosphate and phenylthio or phenoxy or phenylamino. It not only has a high refractive index, a high Abbe number, and good light transmittance, but also benefits from the freely rotatable single bond centered on phosphorus. This structural characteristic gives the material good flexibility and toughness, enabling it to deform when subjected to external force without being easily broken, and has good mechanical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained like these drawings without paying any creative work.

[0045] Figure 1 It is the general structural formula of the compound proposed in this application.

[0046] Figure 2 It is a schematic diagram of the reaction principle for preparing the P1 compound proposed in this application.

[0047] Figure 3 It is a schematic diagram of the reaction principle for preparing P2 compound proposed in this application.

[0048] Figure 4 It is a schematic diagram of the reaction principle for preparing the P3 compound proposed in this application.

[0049] Figure 5 It is a schematic diagram of the reaction principle for preparing the P4 compound proposed in this application.

[0050] Figure 6 It is a schematic diagram of the reaction principle for preparing the P5 compound proposed in this application.

[0051] Figure 7 It is a schematic diagram of the reaction principle for preparing the P6 compound proposed in this application.

[0052] Figure 8 It is a schematic diagram of the reaction principle for preparing the P7 compound proposed in this application.

[0053] Fig. 9 It is a schematic diagram of the process for preparing the compound proposed in this application. DETAILED DESCRIPTION

[0054] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0055] It should also be understood that the terms used in this application specification are only for the purpose of describing specific embodiments and are not intended to limit the application. As used in this application specification and the appended claims, unless the context clearly indicates otherwise, the singular forms "a", "an" and "the" are intended to include plural forms.

[0056] It should be further understood that the term “and / or” used in the specification and appended claims refers to any combination and all possible combinations of one or more of the associated listed items, and includes these combinations.

[0057] Optical materials are mainly divided into two categories: glass and resin, and are widely used in many fields such as display, lens, sensor, etc. Among them, optical resin materials are gaining more and more attention in the field of optical materials.

[0058] For example, high refractive index modified polyphenylene sulfide material, but this material lacks flexible groups, so the material is very brittle and is not suitable for direct application in the optical field.

[0059] Therefore, an embodiment of the present application provides a compound, which mainly comprises two structural units, namely, phosphate ester and phenylthio or phenoxy or phenylamino. It not only has a high refractive index, a high Abbe number, and good light transmittance, but also benefits from the freely rotatable single bond centered on phosphorus. This structural characteristic gives the material good flexibility and toughness, enabling it to deform when subjected to external force without being easily broken, and has good mechanical properties.

[0060] The compounds provided in the examples of the present application have the following general formula:

[0061]

[0062] Wherein, X can be an element of the sixth main group; R1 can be -O-, -S- or -NH-; R2 can be a benzene ring group, a phenyl sulfide group or a sulfide group; R3, R4, R5 and R6 can be one of a hydrogen atom, a sulfide group, an ether group, a mercapto group and a phenolic hydroxyl group; n and m are integers, 0≤n≤5, 1≤m≤10. Wherein, R3, R4, R5 and R6 can be of the same structure or different structures.

[0063] For example, n can be any value between 0 and 5, such as 0, 1, 2, 3, 4, 5, etc. Since too many phenyl sulfide structural units will reduce the structural proportion of phosphate esters and weaken the flexibility and other properties imparted by the phosphate ester structure. Therefore, n is limited to the range of 0 to 5, while increasing the refractive index, the structural proportion of phosphate esters is avoided from being reduced, so that the prepared compound maintains good flexibility and toughness.

[0064] Exemplarily, m can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc., any value between 1 and 10.

[0065] The compound proposed in the embodiment of the present application mainly comprises two structural units of phosphate and phenylthio or phenoxy or phenylamino, because the structure contains a large number of high molar refractive index groups. These groups can be phosphorus, sulfur, selenium and benzene ring, etc. These elements or groups, due to their special electronic structure and atomic radius, slow down the propagation speed of light when passing through these materials, thereby increasing the refractive index. In addition, +5 valence phosphorus plays a key role in the resin. Due to the high valence state of phosphorus, it can bridge up to four sulfur atoms at the same time, forming a structure with an ultra-high refractive index. This structure not only increases the density of the resin, but also makes the propagation path of light therein more tortuous, thereby further increasing the refractive index. And thanks to the freely rotatable single bond centered on phosphorus, this structural characteristic gives the material good flexibility and toughness, so that it can be deformed and not easily broken when subjected to external force, and has good mechanical properties, especially large impact strength.

[0066] On the other hand, phenylthio, phenoxy or phenylamino are also important factors in increasing the refractive index. Phenylthio, phenoxy or phenylamino themselves have a high refractive index, and new groups can be introduced on the benzene ring to further increase the refractive index. These new groups can affect the electron cloud distribution of the benzene ring through conjugation effect or induction effect, so that the propagation speed of light slows down when passing through, and the refractive index increases.

[0067] Moreover, there is no conjugated π bond in the phosphate structure. A higher phosphate ratio can increase the Abbe number of the resin. Specifically, a higher phosphate ratio means that more groups in the resin are phosphates rather than other groups that may introduce dispersion (such as conjugated π bonds, etc.), so the dispersion ability of the resin is reduced and the Abbe number is increased.

[0068] The compounds of the embodiments of the present application also have good light transmittance. On the one hand, there is no light absorption in the phosphate ester and phenylthio or phenoxy or phenylamino groups in the resin, which means that light will not be significantly absorbed when passing through these groups, thereby ensuring the high transmittance of light in the resin. On the other hand, the spatial orientation of thio / selenophosphate is random, which is also very important for the light transmittance of the resin. Since the spatial orientation of these groups is not ordered, they are not easy to form a large-area π-conjugated structure. π-conjugated structure usually leads to the delocalization of electrons in the molecule, which may cause the absorption of light. However, in the resin, since the spatial orientation of these groups is random, they cannot effectively form a large-area π-conjugated structure, so strong light absorption will not be produced. On the contrary, this randomly oriented group forms a randomly stacked amorphous structure in the resin. This structure not only does not hinder the transmission of light, but may make the propagation of light in the resin more uniform by scattering and other means. Therefore, the resin can maintain good light transmittance, so that light can maintain high brightness and clarity when passing through the resin. In addition, the compounds of the embodiments of the present application also have high Tg (glass transition temperature) and low water absorption.

[0069] In an optional embodiment, X can be selected from any substituent of three common sixth main group elements: O, S and Se, which is easy to implement in terms of process and reduces production costs.

[0070] In an alternative embodiment, the compound may include a P1 compound (eg Figure 2 As shown), P2 compound (such as Figure 3 As shown), P3 compound (as Figure 4 As shown), P4 compound (such as Figure 6 As shown) and P5 compound (as Figure 6 As shown), P6 compound (as Figure 7 As shown) and P7 compound (as Figure 8Of course, in other embodiments, the compound may also be other structures, mainly comprising two structural units of phosphate and phenylthio or phenoxy or phenylamino, within the scope of the above general formula.

[0071] As an embodiment, the structural formula of the P1 compound may be:

[0072]

[0073] Among them, the refractive index of the P1 compound is 1.724, which has a high refractive index. In the field of AR glasses display, the P1 compound as a resin material has a high refractive index, which can effectively improve the light efficiency, reduce the thickness of the lens, reduce the cost and obtain a good wearing experience.

[0074] As an embodiment, the structural formula of the P2 compound may be:

[0075]

[0076] Among them, the refractive index of the P2 compound is 1.786, which has a high refractive index. In the field of AR glasses display, the P2 compound as a resin material has a high refractive index, which can effectively improve the light efficiency, reduce the thickness of the lens, reduce the cost and obtain a good wearing experience.

[0077] As an embodiment, the structural formula of the P3 compound may be:

[0078]

[0079] Among them, the refractive index of the P3 compound is 1.762, which has a high refractive index. In the field of AR glasses display, the P3 compound as a resin material has a high refractive index, which can effectively improve the light efficiency, reduce the thickness of the lens, reduce the cost and obtain a good wearing experience.

[0080] As an embodiment, the structural formula of the P4 compound may be:

[0081]

[0082] Among them, the refractive index of the P4 compound is 1.794, which has a high refractive index. In the field of AR glasses display, the P4 compound as a resin material has a high refractive index, which can effectively improve the light efficiency, reduce the thickness of the lens, reduce the cost and obtain a good wearing experience.

[0083] As an embodiment, the structural formula of the P5 compound may be:

[0084]

[0085] Among them, the refractive index of the P5 compound is 1.798, which has a high refractive index. In the field of AR glasses display, the P5 compound as a resin material has a high refractive index, which can effectively improve the light efficiency, reduce the thickness of the lens, reduce the cost and obtain a good wearing experience.

[0086] As an embodiment, the structural formula of the P6 compound may be:

[0087]

[0088] Among them, the refractive index of the P6 compound is 1.686, which has a high refractive index. In the field of AR glasses display, the P6 compound as a resin material has a high refractive index, which can effectively improve the light efficiency, reduce the thickness of the lens, reduce the cost and obtain a good wearing experience.

[0089] As an embodiment, the structural formula of the P7 compound may be:

[0090]

[0091] Among them, the refractive index of the P7 compound is 1.742, which has a high refractive index. In the field of AR glasses display, the P7 compound as a resin material has a high refractive index, which can effectively improve the light efficiency, reduce the thickness of the lens, reduce the cost and obtain a good wearing experience.

[0092] The present application also provides a resin material including the above-mentioned compound. Since the resin material includes the above-mentioned compound, the resin material provided in the present application has the properties and beneficial effects of the above-mentioned compound, which will not be described one by one here.

[0093] The embodiment of the present application also provides an application of resin materials in optical waveguide technology. For example, in the field of AR glasses display, the optical waveguide technology based on the diffraction principle uses resin materials as a substrate, and realizes the coupling, total reflection propagation and coupling out of light through a grating with a specific structure, thereby transmitting the light signal emitted by the image source to the human eye to form a virtual image. In the field of AR glasses display, the resin material has a higher refractive index, which can effectively improve the light efficiency, reduce the thickness of the lens, reduce the cost and obtain a good wearing experience.

[0094] The present invention also provides a method for preparing a compound, the method comprising:

[0095] S1, providing a first monomer and a second monomer;

[0096] S2, mixing the first monomer and the second monomer and performing a polymerization reaction to obtain a compound;

[0097] Wherein, the general formula of the first monomer is as follows:

[0098]

[0099] Wherein, Y is an amino group, a hydroxyl group or a thiol group, and n is an integer, 0≤n≤5;

[0100] The general formula of the second monomer is as follows:

[0101]

[0102] Among them, R7 is a halogen atom, and R2 is a benzene ring group, a phenylthioether group or a thioether group.

[0103] The preparation method of the compound proposed in the examples of the present application has simple steps and reduces the process difficulty and production cost.

[0104] In an alternative embodiment, R7 is a chlorine, bromine or iodine atom.

[0105] In an optional embodiment, the first monomer is at least one selected from 4,4-dihydroxydiphenyl sulfide, 1,4-phenyldithiol, 4,4'-diaminodiphenyl sulfide and 4,4'-diamino(2,2'-methylthio)diphenyl sulfide.

[0106] In an optional embodiment, the second monomer is selected from at least one of phenylthiophosphoryl dichloride, phenylthiophosphoryl dichloride, phenylphosphoryl dichloride and phenylselenophosphoryl dichloride.

[0107] In an optional embodiment, the first monomer and the second monomer are mixed and subjected to polymerization reaction to obtain a compound, including: the first monomer, the second monomer, a catalyst and a solvent are mixed and subjected to polymerization reaction to obtain a compound.

[0108] In an optional embodiment, the catalyst is selected from at least one of triethylamine, 1-methylimidazole, anhydrous potassium carbonate, and potassium iodide.

[0109] In an optional embodiment, the solvent is at least one of dichloromethane and acetone.

[0110] In an optional embodiment, the first monomer, the second monomer, the catalyst and the solvent are mixed and subjected to a polymerization reaction to obtain a compound, including:

[0111] Mixing a first monomer, a second monomer, a catalyst and a solvent and performing a polymerization reaction to obtain a reaction mixture including a compound;

[0112] The reaction mixture is stirred and the solvent is removed to obtain a viscous mass;

[0113] The viscous material is precipitated, washed and then vacuum dried to obtain a compound.

[0114] As an implementation method, the first monomer can be 4,4-dihydroxydiphenyl sulfide, the second monomer can be phenylthiophosphoryl dichloride, the catalyst can be triethylamine and 1-methylimidazole, and the solvent can be dichloromethane. Specifically, the weights of the above components are as follows: 4,4-dihydroxydiphenyl sulfide 3.008g; phenylthiophosphoryl dichloride 2.908g; triethylamine 4.8mL; 1-methylimidazole 0.0329mL; dichloromethane 21mL.

[0115] As an embodiment, the first monomer can be 1,4-phenyldithiol, the second monomer can be phenylthiophosphoryl dichloride, the catalyst can be triethylamine and 1-methylimidazole, and the solvent can be dichloromethane. Specifically, the weights of the above components are as follows: 1,4-phenyldithiol 1.96g; phenylthiophosphoryl dichloride 2.908g; triethylamine 4.8mL; 1-methylimidazole 0.0329mL; dichloromethane 21mL.

[0116] As an embodiment, the first monomer can be 4,4'-diaminodiphenyl sulfide, the second monomer can be phenylthiophosphoryl dichloride, the catalyst can be anhydrous potassium carbonate and potassium iodide, and the solvent can be acetone. Specifically, the weight of the above components is as follows: 4,4'-diaminodiphenyl sulfide 2.163g; phenylthiophosphoryl dichloride 2.532g; anhydrous potassium carbonate 2.07g; potassium iodide 0.166g; acetone 30mL.

[0117] As an embodiment, the first monomer can be 4,4'-diamino (2,2'-methylthio) diphenyl sulfide, the second monomer can be phenylthiophosphoryl dichloride, the catalyst can be anhydrous potassium carbonate and potassium iodide, and the solvent can be acetone. Specifically, the weight of the above components is as follows: 4,4'-diamino (2,2'-methylthio) diphenyl sulfide 3.085g; phenylthiophosphoryl dichloride 2.532g; anhydrous potassium carbonate 2.07g; potassium iodide 0.166g; acetone 30mL.

[0118] As an implementation method, the first monomer can be 4,4'-diaminodiphenyl sulfide, the second monomer can be phenylthiophosphonothioic acid dichloride, the catalyst can be anhydrous potassium carbonate and potassium iodide, and the solvent can be acetone. Specifically, the weight of the above components is as follows: 4,4'-diaminodiphenyl sulfide 2.163g; phenylthiophosphonothioic acid dichloride 2.917g; anhydrous potassium carbonate 2.07g; potassium iodide 0.166g; acetone 30mL.

[0119] Wherein, the structural formula of phenylthiophosphonothioic acid dichloride is as follows:

[0120] The compound of the present application is synthesized by using phenylthiophosphonothioic acid dichloride as a monomer, so that the refractive index thereof can be made higher.

[0121] As an implementation method, the first monomer can be 4,4-dihydroxydiphenyl sulfide, the second monomer can be phenylphosphoryl dichloride, the catalyst can be triethylamine and 1-methylimidazole, and the solvent can be dichloromethane. Specifically, the weights of the above components are as follows: 4,4-dihydroxydiphenyl sulfide 3.008g; phenylphosphoryl dichloride 2.673g; triethylamine 4.8mL; 1-methylimidazole 0.0329mL; dichloromethane 21mL.

[0122] As an implementation method, the first monomer can be 4,4-dihydroxydiphenyl sulfide, the second monomer can be phenyl selenophosphoryl dichloride, the catalyst can be triethylamine and 1-methylimidazole, and the solvent can be dichloromethane. Specifically, the weights of the above components are as follows: 4,4-dihydroxydiphenyl sulfide 3.008g; phenyl selenophosphoryl dichloride 3.555g; triethylamine 4.8mL; 1-methylimidazole 0.0329mL; dichloromethane 21mL.

[0123] Among them, the structural formula of phenylselenophosphoryl dichloride is as follows:

[0124] The compound of the present application is synthesized by using phenylthiophosphonothioic acid dichloride as a monomer, so that the refractive index thereof can be made higher.

[0125] In some embodiments, the reaction mixture is stirred at ambient temperature for 3 hours to 5 hours. For example, the reaction mixture may be stirred for 3 hours, 4 hours, or 5 hours, etc., to facilitate the reaction.

[0126] In some embodiments, the viscous material is precipitated and then washed with methanol or ethanol.

[0127] In some embodiments, the viscous object is precipitated, washed, and then dried in a vacuum oven, the temperature is set to 70°C-90°C, and the vacuum drying is performed for 10 hours to 15 hours. Exemplarily, in step S5, the temperature can be set to 7°C, 8°C, or 9°C, and the vacuum drying is performed for 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, or 15 hours, etc. to form a compound.

[0128] As an implementation method, Figure 2 As shown, the P1 compound can be generated by reacting 4,4-dihydroxydiphenyl sulfide and phenylthiophosphoryl dichloride. The structure of the generated P1 compound is as follows:

[0129]

[0130] As an implementation method, Figure 3 As shown, the P2 compound can be generated by the reaction of 1,4-phenyldithiol and phenylthiophosphoryl dichloride. The structure of the generated P2 compound is as follows:

[0131]

[0132] As an implementation method, Figure 4 As shown, the P3 compound can be generated by reacting 4,4'-diaminodiphenyl sulfide and phenylthiophosphoryl dichloride. The structure of the generated P3 compound is as follows:

[0133]

[0134] As an implementation method, Figure 5 As shown, the P4 compound can be generated by reacting 4,4'-diamino(2,2'-methylthio)diphenyl sulfide and phenylthiophosphoryl dichloride. The structure of the generated P4 compound is as follows:

[0135]

[0136] As an implementation method, Figure 6 As shown, the P5 compound can be generated by reacting 4,4'-diaminodiphenyl sulfide and phenylthiophosphonothioic acid dichloride. The structure of the generated P5 compound is as follows:

[0137]

[0138] As an implementation method, Figure 7 As shown, the P6 compound can be generated by reacting 4,4-dihydroxydiphenyl sulfide and phenylphosphinoyl dichloride. The structural formula of the generated P6 compound is as follows:

[0139]

[0140] As an implementation method, Figure 8 As shown, the P7 compound can be generated by reacting 4,4-dihydroxydiphenyl sulfide and phenylselenophosphoryl dichloride. The structure of the generated P7 compound is as follows:

[0141]

[0142] The compounds of the present invention are further described below in conjunction with specific examples and test data.

[0143] Example 1

[0144] Synthesis of P1 compound:

[0145] like Figure 2As shown, 4,4-dihydroxydiphenyl sulfide (3.008 g, 13.78 mmol), triethylamine (4.8 mL, 34.45 mmol), dichloromethane (21 mL) and 1-methylimidazole (0.0329 mL, 0.413 mmol) were added to a 100 mL reaction bottle under stirring at room temperature. After cooling to 0°C, phenylthiophosphoryl dichloride (2.908 g, 13.78 mmol) in dichloromethane was added dropwise to allow the polymerization reaction to proceed. After the addition was completed, the reaction mixture was stirred at ambient temperature for 4 hours. The solvent of the resulting mixture was removed under reduced pressure to obtain a viscous object. The viscous object was precipitated with methanol and washed three times. The resulting product was dried in a vacuum oven, the temperature was set to 80°C, and vacuum dried for 12 hours to form the P1 compound.

[0146] The H NMR spectrum of compound P1 is: 1 H NMR (400MHZ, CDCl3) 7.20-7.35ppm (m, 9H), 6.60ppm (m, 4H).

[0147] Example 2

[0148] Synthesis of P2 compound:

[0149] like Figure 3 As shown, 1,4-phenyldithiol (1.960 g, 13.78 mmol), triethylamine (4.8 mL, 34.45 mmol), dichloromethane (21 mL) and 1-methylimidazole (0.0329 mL, 0.413 mmol) were added to a 100 mL reaction bottle under stirring at room temperature. After cooling to 0 ° C, phenylthiophosphoryl dichloride (2.908 g, 13.78 mmol) in dichloromethane was added dropwise to allow the polymerization reaction to proceed. After the addition was completed, the reaction mixture was stirred at ambient temperature for 4 hours. The solvent of the resulting mixture was removed under reduced pressure to obtain a viscous object. The viscous object was precipitated with methanol and washed three times. The resulting product was dried in a vacuum oven, the temperature was set to 80 ° C, and vacuum dried for 12 hours to form the P2 compound.

[0150] The H NMR spectrum of compound P2 is: 1 H NMR (400MHZ, CDCl3) 7.31ppm (m, 2H), 7.20~7.26ppm (m, 5H), 7.16ppm (d, 2H).

[0151] Example 3

[0152] Synthesis of P3 compounds:

[0153] like Figure 4As shown, 4,4'-diaminodiphenyl sulfide (2.163 g, 10 mmol), phenylthiophosphoryl dichloride (2.532 g, 12 mmol), anhydrous potassium carbonate (2.07 g, 15 mmol) and potassium iodide (0.166 g, 1 mmol) were added to acetone (30 mL). The mixture was heated to reflux at 56 °C for 2-3 hours, and then the solvent was removed by rotary evaporation. Aqueous potassium carbonate solution (5% w / v, 50 mL) was added to the mixture and stirred for 2 hours. The viscous mass was filtered and then washed three times with methanol. The resulting product was dried in a vacuum oven, the temperature was set to 80 °C, and vacuum dried for 12 hours to form P3 compound.

[0154] The H NMR spectrum of compound P3 is: 1 H NMR (400MHZ, CDCl3) 7.25~7.31ppm (m, 5H), 7.07ppm (d, 4H), 6.70ppm (s, 2H), 6.60ppm (d, 4H).

[0155] Example 4

[0156] Synthesis of P4 compounds:

[0157] like Figure 5 As shown, 4,4'-diamino(2,2'-methylthio)diphenyl sulfide (3.085 g, 10 mmol), phenylthiophosphoryl dichloride (2.532 g, 12 mmol), anhydrous potassium carbonate (2.07 g, 15 mmol) and potassium iodide (0.166 g, 1 mmol) were added to acetone (30 mL). The mixture was heated to reflux at 56 °C for 2-3 hours, and then the solvent was removed by rotary evaporation. Aqueous potassium carbonate solution (5% w / v, 50 mL) was added to the mixture and stirred for 2 hours. The viscous mass was filtered and then washed three times with methanol. The resulting product was dried in a vacuum oven, the temperature was set to 80 °C, and vacuum dried for 12 hours to form P4 compound.

[0158] The H NMR spectrum of compound P4 is: 1 H NMR (400MHZ, CDCl3)7.25~7.31ppm(m,5H),7.10~7.20ppm(m,4H),6.70ppm(s,2H),6.36ppm(d,2H),2.46ppm(s,6H).

[0159] Example 5

[0160] Synthesis of P5 compound:

[0161] like Figure 6As shown, 4,4'-diaminodiphenyl sulfide (2.163 g, 10 mmol), phenylthiophosphonothioic acid dichloride (2.917 g, 12 mmol), anhydrous potassium carbonate (2.07 g, 15 mmol) and potassium iodide (0.166 g, 1 mmol) were added to acetone (30 mL). The mixture was heated to reflux at 56 °C for 2-3 hours, and then the solvent was removed by rotary evaporation. Aqueous potassium carbonate solution (5% w / v, 50 mL) was added to the mixture and stirred for 2 hours. The viscous mass was filtered and then washed three times with methanol. The resulting product was dried in a vacuum oven, the temperature was set to 80 °C, and vacuum dried for 12 hours to form P5 compound.

[0162] The H NMR spectrum of compound P5 is: 1 H NMR (400MHZ, CDCl3) 7.24~7.36ppm (m, 5H), 7.07ppm (d, 4H), 6.60~6.70ppm (m, 6H).

[0163] Example 6

[0164] Synthesis of P6 compound:

[0165] like Figure 7 As shown, 4,4-dihydroxydiphenyl sulfide (3.008 g, 13.78 mmol), triethylamine (4.8 mL, 34.45 mmol), dichloromethane (21 mL) and 1-methylimidazole (0.0329 mL, 0.413 mmol) were added to a 100 mL reaction bottle under stirring at room temperature. After cooling to 0 ° C, a dichloromethane solution of phenylphosphoryl dichloride (2.673 g, 13.78 mmol) was added dropwise to allow the polymerization reaction to proceed. After the addition was completed, the reaction mixture was stirred at ambient temperature for 4 hours. The solvent of the resulting mixture was removed under reduced pressure to obtain a viscous object. The viscous object was precipitated with methanol and washed three times. The resulting product was dried in a vacuum oven, the temperature was set to 80 ° C, and vacuum dried for 12 hours to form a P6 compound.

[0166] The H NMR spectrum of compound P6 is: 1 H NMR (400MHZ, CDCl3) 7.39ppm (d, 4H), 7.26ppm (m, 5H), 7.08ppm (d, 4H).

[0167] Example 7

[0168] Synthesis of P7 compound:

[0169] like Figure 8As shown, 4,4-dihydroxydiphenyl sulfide (3.008 g, 13.78 mmol), triethylamine (4.8 mL, 34.45 mmol), dichloromethane (21 mL) and 1-methylimidazole (0.0329 mL, 0.413 mmol) were added to a 100 mL reaction bottle under stirring at room temperature. After cooling to 0 ° C, a dichloromethane solution of phenyl selenophosphoryl dichloride (3.555 g, 13.78 mmol) was added dropwise to allow the polymerization reaction to proceed. After the addition was completed, the reaction mixture was stirred at ambient temperature for 4 hours. The solvent of the resulting mixture was removed under reduced pressure to obtain a viscous object. The viscous object was precipitated with methanol and washed three times. The resulting product was dried in a vacuum oven, the temperature was set to 80 ° C, and vacuum dried for 12 hours to form the P7 compound.

[0170] The H NMR spectrum of compound P7 is: 1 H NMR (400MHZ, CDCl3) 7.24~7.31ppm (m, 5H), 7.21ppm (d, 4H), 6.61ppm (d, 4H).

[0171] The compounds prepared in Examples 1 to 7 above were subjected to the following tests.

[0172] 1. Refractive index test. The purified resin is dispersed in a polar solvent such as tetrachloroethane, and then spin-coated on a silicon wafer. After baking in an oven, the refractive index is tested using an ellipsometer. The Abbe number is calculated using the refractive index at wavelengths of 486.1nm, 587.6nm, and 656.3nm. The calculation formula is as follows:

[0173]

[0174] The refractive index and Abbe number of the compounds prepared in Examples 1 to 7 are shown in Table 1.

[0175] 2. Water absorption test. The compound prepared in each example was injected into a plate-shaped molded piece with a thickness of 2 mm, and the water absorption after immersion at 23°C for 24 hours was measured according to ISO62. The water absorption of the compounds prepared in Examples 1 to 7 was shown in Table 1.

[0176] 3. Transmittance test. The purified resin is dispersed in a polar solvent, such as tetrachloroethane, and then spin-coated on the surface of a glass substrate by spin coating. After baking in an oven, the transmittance meter is used for testing. The transmittances of the compounds prepared in Examples 1 to 7 are shown in Table 1.

[0177] 4. Glass transition temperature (Tg) was tested using a 2910 differential scanning calorimeter manufactured by TA Instruments Japan at a heating rate of 10°C / min. The glass transition temperatures (Tg) of the compounds prepared in Examples 1 to 7 are shown in Table 1.

[0178] 5. The prepreg obtained in each example was cut using a profiling machine to obtain a sample with a height of 63 mm, a width of 13 mm, and a thickness of 2.8 mm. A notch was formed at a height of 32 mm on the sample to obtain a test piece. The cantilever beam impact strength of the test piece was measured using a cantilever beam impact tester (manufactured by Toyo Seiki Co., Ltd.) under the conditions of hammer capacity: 2.75 J, hammer weight: 13.97 N, distance from the axis to the center of gravity: 10.54 cm, and distance from the axis to the impact point: 33.5 cm. The test data of the compounds obtained in Examples 1 to 7 are shown in Table 1.

[0179] The experimental comparison data and analysis are as follows:

[0180] Table 1

[0181]

[0182] As shown in the table above: the compounds prepared in Examples 1 to 5 all have high refractive index, high Abbe number, good light transmittance, high Tg (glass transition temperature) and low water absorption. In addition, the compounds in the examples of the present application also have good flexibility and toughness, good impact resistance, and good mechanical properties.

[0183] Those skilled in the art may combine and associate different embodiments or examples and features of different embodiments or examples described in this specification without mutual contradiction.

[0184] The above is only a specific implementation of the present application, but the protection scope of the present application is not limited thereto. Any technician familiar with the technical field can easily think of various equivalent modifications or replacements within the technical scope disclosed in the present application, and these modifications or replacements should be included in the protection scope of the present application. Therefore, the protection scope of the present application shall be based on the protection scope of the claims.

Claims

1. A compound, characterized in that The compound has the following general formula: Among them, X is a sixth main group element; R1 is -O-, -S- or -NH-; R2 is a benzene ring group, a phenylthioether group or a thioether group; R3, R4, R5 and R6 are each selected from one of a hydrogen atom, a thioether group, an ether group, a mercapto group and a phenolic hydroxyl group; n and m are integers, 0≤n≤5, 1≤m≤10.

2. The compound according to claim 1, characterized in that X is any substituent selected from -O-, -S-, and -Se-.

3. The compound according to claim 2, characterized in that The structural formula of the compound is as follows: or, or, or, or, or, or, 4. A resin material, characterized in that: The resin material comprises the compound according to any one of claims 1 to 3.

5. Use of the resin material according to claim 4 in optical waveguide technology.

6. A method for preparing the compound according to any one of claims 1 to 3, characterized in that: The preparation method comprises: providing a first monomer and a second monomer; The first monomer and the second monomer are mixed and subjected to a polymerization reaction to obtain the compound; Wherein, the general formula of the first monomer is as follows: Wherein, Y is an amino group, a hydroxyl group or a thiol group, and n is an integer, 0≤n≤5; The general formula of the second monomer is as follows: Among them, R7 is a halogen atom, and R2 is a benzene ring group, a phenylthioether group or a thioether group.

7. The preparation method according to claim 6, characterized in that: R7 is a chlorine, bromine or iodine atom.

8. The preparation method according to claim 6, characterized in that: The first monomer is at least one selected from 4,4-dihydroxydiphenyl sulfide, 1,4-phenyldithiol, 4,4'-diaminodiphenyl sulfide and 4,4'-diamino(2,2'-methylthio)diphenyl sulfide.

9. The preparation method according to claim 6, characterized in that: The second monomer is selected from at least one of phenylthiophosphoryl dichloride, phenylthiophosphoryl dichloride, phenylphosphoryl dichloride and phenylselenophosphoryl dichloride.

10. The preparation method according to claim 6, characterized in that: The step of mixing the first monomer and the second monomer and performing a polymerization reaction to obtain the compound comprises: The first monomer, the second monomer, a catalyst and a solvent are mixed and subjected to a polymerization reaction to obtain the compound.

11. The preparation method according to claim 10, characterized in that: The catalyst is selected from at least one of triethylamine, 1-methylimidazole, anhydrous potassium carbonate and potassium iodide.

12. The preparation method according to claim 10, characterized in that: The solvent is selected from at least one of dichloromethane and acetone.

13. The preparation method according to claim 10, characterized in that: The first monomer, the second monomer, a catalyst and a solvent are mixed and subjected to a polymerization reaction to obtain the compound, comprising: The first monomer, the second monomer, a catalyst and a solvent are mixed and subjected to a polymerization reaction to obtain a reaction mixture including the compound; The reaction mixture is stirred and the solvent is removed to obtain a viscous substance; The viscous object is precipitated, washed and then vacuum dried to obtain the compound.

14. The preparation method according to claim 13, characterized in that: After the viscous object is precipitated, it is washed with methanol or ethanol; and / or, The viscous object is precipitated, washed and then dried in a vacuum oven at a temperature of 70° C. to 90° C. for 10 to 15 hours.

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