Thermoplastic resin and preparation method therefor, and optical product

Abstract

Provided in the embodiments of the present application are a thermoplastic resin and a preparation method therefor, and an optical product. The thermoplastic resin comprises a repeating unit as represented by formula (1), wherein in formula (1), R1 is a substituted or unsubstituted polycyclic arylene group or a substituted or unsubstituted polycyclic heteroarylene group, and R2 is a substituted or unsubstituted phenylene group, a substituted or unsubstituted polycyclic arylene group, a substituted or unsubstituted monocyclic heteroarylene group, or a substituted or unsubstituted polycyclic heteroarylene group; and m1 and m2 are each independently integers from 0 to 10. The thermoplastic resin has a high refractive index, a high Abbe value and a suitable glass transition temperature Tg, and can be prepared by means of a reaction at room temperature; and the preparation process thereof is simple, and is compatible with existing injection molding processes, and the thermoplastic resin can be easily processed into various optical products meeting application requirements.

Description

Thermoplastic resins, their preparation methods and optical products

[0001] This application claims priority to Chinese Patent Application No. 202411816008.5, filed on December 11, 2024, entitled "Thermoplastic Resin and Preparation Method Thereof and Optical Articles Thereof", the entire contents of which are incorporated herein by reference. Technical Field

[0002] This application relates to the field of optical resin technology, and in particular to a thermoplastic resin, its preparation method, and optical products. Background Technology

[0003] Optical resins are widely used in the manufacture of optical lenses, optical guides, optical thin films, and other optical products due to their advantages such as light weight, impact resistance, high transparency, and ease of processing and molding. However, with the increasing pursuit of high optical performance in optical products and considering factors such as process difficulty and production cost, it is necessary to develop optical resin materials that combine high refractive index, high Abbe number, and suitable glass transition temperature (Tg), while also being simple to manufacture and easy to process and mold, in order to better meet the application requirements of optical products. Summary of the Invention

[0004] In view of this, embodiments of this application provide a thermoplastic resin, a method for preparing the same, and an optical product. The thermoplastic resin has a high refractive index, a high Abbe number, and a suitable glass transition temperature (Tg). It can be prepared by reaction at room temperature, the preparation process is simple, it is compatible with existing injection molding processes, and it is easy to process into various optical products that meet application requirements.

[0005] In a first aspect, embodiments of this application provide a thermoplastic resin, the thermoplastic resin comprising repeating units as shown in formula (1),

[0006] In formula (1), R1 is a substituted or unsubstituted polycyclic arylene or a substituted or unsubstituted polycyclic heteroarylene, R2 is a substituted or unsubstituted phenylene, a substituted or unsubstituted polycyclic arylene, a substituted or unsubstituted monocyclic heterocyclic group or a substituted or unsubstituted polycyclic heteroarylene; m1 and m2 are independent integers from 0 to 10.

[0007] The thermoplastic resin provided in this application includes a repeating unit as shown in formula (1). This repeating unit is obtained by reacting a glycol acrylate monomer with a dithiol monomer. It also includes a polycyclic aromatic structure and a sulfur-containing structure. Under the synergistic effect of the various parts of the repeating unit with this unique structure, the thermoplastic resin can have a high refractive index, a high Abbe number, and a suitable glass transition temperature Tg. Moreover, this unique structure makes the thermoplastic resin compatible with existing injection molding processes. It does not require special injection molding equipment and can be processed and molded using existing injection molding equipment, making it easy to obtain various optical products that meet application requirements. In addition, the thermoplastic resin with the above structure can be prepared by reacting a glycol acrylate monomer with a dithiol monomer at room temperature via a thio-ene click reaction. The preparation process is simple and does not require the control of water and oxygen as in free radical polymerization, nor does it require high temperature conditions. The reaction can be carried out at room temperature, which is conducive to industrial production and reduces production difficulty and cost.

[0008] In the embodiments of this application, R1 and R1 are divalent groups, wherein the polycyclic aryl group is a divalent polycyclic aromatic group having multiple (two or more) benzene rings; the polycyclic heteroaryl group is a divalent polycyclic aromatic group containing heteroatoms (e.g., O, S) having multiple (two or more) aromatic rings (including benzene rings or heterocyclic aromatic rings), at least one of the multiple aromatic rings being a heterocyclic aromatic ring.

[0009] In this embodiment, the substituted or unsubstituted polycyclic aryl group comprises 2-10 benzene rings. A suitable number of benzene rings is beneficial for achieving a high refractive index in the resin composition, while maintaining the glass transition temperature (Tg) of the thermoplastic resin at a moderate value. This makes the thermoplastic resin both easy to process and mold, and also improves the thermal stability of the resulting optical articles.

[0010] In the embodiments of this application, the substituted or unsubstituted polycyclic aryl groups include substituted or unsubstituted naphthylene, substituted or unsubstituted anthraceneylene, substituted or unsubstituted phenanthylene, substituted or unsubstituted pyreneylene, substituted or unsubstituted tetraphenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted binatylene, substituted or unsubstituted isopropylbenzinathylene, substituted or unsubstituted fluorene, substituted or unsubstituted spirofluorene, substituted or unsubstituted diphenylfluorene, substituted or unsubstituted dinaphthylfluorene, substituted or unsubstituted dithionylene, substituted or unsubstituted dithionylene, substituted or unsubstituted spirofluoreneanthylene, or substituted or unsubstituted spirofluorenepentaphenylene. The introduction of multiple benzene ring structures is beneficial for increasing the refractive index of thermoplastic resins and also for raising the glass transition temperature (Tg) of thermoplastic resins.

[0011] In this embodiment, the substituted or unsubstituted polycyclic heteroaryl group comprises 2-10 aromatic rings. A suitable number of aromatic rings is beneficial for achieving a high refractive index in the resin composition, while maintaining the glass transition temperature (Tg) of the thermoplastic resin at a moderate value. This makes the thermoplastic resin both easy to process and mold, and also improves the thermal stability of the resulting optical articles.

[0012] In the embodiments of this application, the substituted or unsubstituted polycyclic heteroaryl groups include substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted thieno[3,2-b]thienophene, substituted or unsubstituted groups of formula (a), substituted or unsubstituted groups of formula (b), and substituted or unsubstituted groups of formula (c).

[0013] Ar1 and Ar2 are independently selected from aromatic rings or aromatic heterocyclic rings, and at least one of Ar1 and Ar2 is an aromatic heterocyclic ring; L1 and L2 are selected from O, S, Se, and -N(R) respectively. a )-、-P(R b )-、-P(=O)(R c )-, or -Si(R d )-, R a R b R c R d They are aryl or alkyl, respectively; Indicates the connection site.

[0014] In the embodiments of this application, the substituted or unsubstituted monocyclic heterocyclic group includes substituted or unsubstituted dioxane hexacyclic group, substituted or unsubstituted dithiohexacyclic group, substituted or unsubstituted trioxane hexacyclic group, substituted or unsubstituted trithiaalkyl group, substituted or unsubstituted furanyl group, or substituted or unsubstituted thiophene group.

[0015] In the embodiments of this application, the substituent groups in the substituted polycyclic aryl group, substituted polycyclic heteroaryl group, substituted phenylene group, and substituted monocyclic heterocyclic group include one or more of halogen atoms, hydroxyl groups, cyano groups, amino groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkoxy groups, and phenyl groups.

[0016] In this embodiment, R1 comprises a spirocyclic structure or a naphthalene ring structure; and / or, R2 is a substituted or unsubstituted polycyclic aryl group, or a substituted or unsubstituted polycyclic heteroaryl group. The spirocyclic structure comprises multiple aromatic rings, possesses a large three-dimensional spatial structure, and exhibits high rigidity, which is beneficial for improving the refractive index and glass transition temperature (Tg) of the thermoplastic resin. The introduction of the naphthalene ring structure into the repeating unit can better improve the refractive index of the thermoplastic resin composition while simultaneously achieving a higher glass transition temperature and a higher Abbe number.

[0017] In this embodiment, R2 contains sulfur atoms. The presence of sulfur atoms in R2 can increase the sulfur content of the thermoplastic resin, thereby better controlling the glass transition temperature (Tg) of the thermoplastic resin and reducing the decay of the Abbe number.

[0018] In this embodiment of the application, R1 includes a naphthalene ring structure, or R2 includes a naphthalene ring structure.

[0019] In this embodiment, R1 comprises a naphthalene ring structure, or R2 comprises a naphthalene ring structure, and R1 comprises a spiro ring structure. This is advantageous for achieving both a high refractive index and an Abbe number, while simultaneously obtaining a higher glass transition temperature Tg.

[0020] In this embodiment of the application, R1 is the group represented by formula (a);

[0021] Ar1 and Ar2 can be independently selected from aromatic rings or heterocyclic aromatic rings. Indicates the connection site. R1 includes spirocyclic and naphthalenecyclic structures, which is beneficial for thermoplastic resins to achieve both high refractive index and Abbe number while obtaining a higher glass transition temperature Tg.

[0022] In the embodiments of this application, R1 is a substituted or unsubstituted polycyclic aryl group, and the substituted or unsubstituted polycyclic heteroaryl group is directly connected to the O atom through the aromatic carbon.

[0023] In R2, the substituted or unsubstituted phenylene, the substituted or unsubstituted polycyclic aryl group, and the substituted or unsubstituted polycyclic heteroaryl group are directly connected to the S atom through the aromatic nucleus carbon.

[0024] In this embodiment of the application, R1 has 8-50 carbon atoms; R2 has 3-50 carbon atoms. Suitable carbon atom numbers allow R1 and R2 to have suitable group sizes.

[0025] In some embodiments of this application, the repeating unit shown in formula (1) includes any one or more of the structures shown in formulas (1-1) to (1-8):

[0026] In this embodiment, the weight-average molecular weight of the thermoplastic resin is 2,000-100,000. The weight-average molecular weight (Mw) of the thermoplastic resin can be obtained by gel permeation chromatography (GPC).

[0027] In this embodiment, the molecular weight distribution index (PDI) of the thermoplastic resin is less than or equal to 1.6. A lower PDI in the thermoplastic resin is beneficial for improving its film-forming properties, obtaining a more uniform resin film, and improving the performance of optical products; a lower PDI is also beneficial for obtaining better flowability, thereby enabling better control of the processing process and reducing processing costs and difficulty.

[0028] In this embodiment, the refractive index of the thermoplastic resin is greater than or equal to 1.66. The refractive index of the thermoplastic resin is the ratio of the speed of light in a vacuum to the speed of light in the thermoplastic resin, and can be represented by n. The higher the refractive index of the material, the stronger its ability to refract incident light. Thermoplastic resin has a high refractive index, which is beneficial to improving the refractive ability of the optical lenses made from it. This helps to improve the sharpness of photographs for camera lenses and improve the clarity of vision for eyeglass lenses. In addition, the high refractive index of thermoplastic resin can further reduce the thickness of optical lenses. The refractive index of the thermoplastic resin can be measured using an Abbe refractometer, an ellipsometer, or a prism coupler.

[0029] In this embodiment, the Abbe number of the thermoplastic resin is greater than or equal to 15. The Abbe number is a physical quantity used to measure the degree of dispersion of a transparent medium. The higher the Abbe number, the lower the dispersion, and the clearer the visual effect of the optical lens made from the thermoplastic resin; conversely, the lower the Abbe number, the more severe the dispersion. The Abbe number of the thermoplastic resin can be measured using an Abbe refractometer, an ellipsometer, or a prism coupler.

[0030] In this embodiment, the glass transition temperature (Tg) of the thermoplastic resin is greater than or equal to 80°C. A relatively high glass transition temperature (Tg) of the thermoplastic resin is beneficial for improving the service reliability of the resulting optical products.

[0031] A second aspect of this application provides a method for preparing a thermoplastic resin, comprising:

[0032] The diol acrylate monomer shown in formula (2) and the dithiol monomer shown in formula (3) are dissolved in an organic solvent, and a click reaction is carried out under a protective atmosphere, with the aid of an initiator and at room temperature to obtain a thermoplastic resin. The thermoplastic resin includes the repeating unit shown in formula (1).

[0033] In formulas (1) and (2), R1 is a substituted or unsubstituted polycyclic aryl group or a substituted or unsubstituted polycyclic heteroaryl group;

[0034] In formulas (1) and (3), R2 is a substituted or unsubstituted phenylene, a substituted or unsubstituted polycyclic aryl group, a substituted or unsubstituted monocyclic heterocyclic group, or a substituted or unsubstituted polycyclic heterocyclic group; m1 and m2 are independent integers from 0 to 10.

[0035] The method for preparing thermoplastic resin provided in this application embodiment can react at room temperature without the need for water and oxygen control. The preparation process is simple, can be synthesized quickly, and can be operated at room temperature throughout, making the method highly safe.

[0036] In this embodiment, the initiator includes triethylamine or an ionic liquid. The ionic liquid may be one or more of the following:

[0037] In the embodiments of this application, the organic solvent includes one or more of tetrahydrofuran (THF), dichloromethane (DCM), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO).

[0038] A third aspect of this application provides a resin composition comprising the thermoplastic resin described in the first aspect or the thermoplastic resin prepared by the preparation method described in the second aspect, and including additives.

[0039] In the embodiments of this application, the additives include one or more of the following: fillers, dyes, antioxidants, anti-yellowing agents, light stabilizers, ultraviolet absorbers, plasticizers, flame retardants, antistatic agents, and release agents.

[0040] In the embodiments of this application, the above-mentioned thermoplastic resin or resin composition can be processed into optical products by various known molding methods, such as injection molding. The thermoplastic resin of the embodiments of this application is compatible with existing injection molding processes, reducing processing difficulty and facilitating industrial applications.

[0041] A third aspect of this application provides an optical article comprising a molded article of the thermoplastic resin described in the first aspect, or a molded article comprising the resin composition described in the third aspect. The optical article may be partially or wholly composed of the molded article of the aforementioned thermoplastic resin or the molded article of the aforementioned resin composition.

[0042] In this application embodiment, the optical product includes an optical lens, an optical film, an optical disc, a light guide plate, or a display panel.

[0043] In this embodiment of the application, the optical lens includes an eyeglass lens, a camera lens, a sensor lens, an illumination lens, an imaging lens, or a lidar lens.

[0044] A fourth aspect of this application provides an apparatus comprising a carrier and an optical article as described in the third aspect, mounted on the carrier. This apparatus may be a mobile terminal, eyeglasses, a camera (such as a camera), a sensing device, a lighting device (such as a desk lamp, ceiling light, street light, etc.), an imaging device (such as an AR / VR imaging device, microscope, telescope, projector, scanner, etc.), a lidar, etc.

[0045] In some embodiments of this application, the mobile terminal includes a device body and a camera module mounted on the device body, the camera module including a lens, and the lens including the optical product described in the third aspect. Attached Figure Description

[0046] Figure 1 is the 1H NMR spectrum of the thermoplastic resin P1 prepared in Example 1 of this application;

[0047] Figure 2 is the 1H NMR spectrum of the thermoplastic resin P2 prepared in Example 2 of this application;

[0048] Figure 3 is the 1H NMR spectrum of the thermoplastic resin P3 prepared in Example 3 of this application;

[0049] Figure 4 is the 1H NMR spectrum of the thermoplastic resin P4 prepared in Example 4 of this application;

[0050] Figure 5 is the 1H NMR spectrum of the thermoplastic resin P5 prepared in Example 5 of this application. Detailed Implementation

[0051] The embodiments of this application will now be described in conjunction with the accompanying drawings.

[0052] High-refractive-index lenses are a crucial component of camera modules. They are typically made from optical resins. Currently, with the increasing pursuit of high optical performance (such as high refractive index and high Abbe number) in high-refractive-index lenses, and considering industrial production requirements such as manufacturing complexity and production costs, it is necessary to develop optical resin materials that possess both high refractive index and high Abbe number, a suitable glass transition temperature (Tg), and a simple manufacturing process that is easy to process and mold. This is to better meet the application needs of high-refractive-index lenses and other optical products. Therefore, this application provides a thermoplastic resin that possesses both high refractive index and high Abbe number, a suitable glass transition temperature (Tg), and can be prepared at room temperature. The manufacturing process is simple, compatible with existing injection molding processes, and easily processed into various optical products that meet application requirements.

[0053] The thermoplastic resin provided in this application embodiment includes the repeating unit shown in formula (1).

[0054] In formula (1), R1 is a substituted or unsubstituted polycyclic arylene or a substituted or unsubstituted polycyclic heteroarylene, R2 is a substituted or unsubstituted phenylene, a substituted or unsubstituted polycyclic arylene, a substituted or unsubstituted monocyclic heterocyclic group or a substituted or unsubstituted polycyclic heteroarylene; m1 and m2 are independent integers from 0 to 10.

[0055] The thermoplastic resin provided in this application includes a repeating unit as shown in formula (1). This repeating unit is obtained by reacting a glycol acrylate monomer with a dithiol monomer. It also includes a polycyclic aromatic structure and a sulfur-containing structure. Under the synergistic effect of the various parts of the repeating unit with this unique structure, the thermoplastic resin can have a high refractive index, a high Abbe number, and a suitable glass transition temperature Tg. Moreover, this unique structure makes the thermoplastic resin compatible with existing injection molding processes. It does not require special injection molding equipment and can be processed and molded using existing injection molding equipment, making it easy to obtain various optical products that meet application requirements. In addition, the thermoplastic resin with the above structure can be prepared by reacting a glycol acrylate monomer with a dithiol monomer at room temperature via a thio-ene click reaction. The preparation process is simple and does not require the control of water and oxygen as in free radical polymerization, nor does it require high temperature conditions. The reaction can be carried out at room temperature, which is conducive to industrial production and reduces production difficulty and cost.

[0056] In this embodiment, the polycyclic aryl group is a divalent polycyclic aromatic group having multiple (two or more) benzene rings, which can be biphenyl aryl, bridged biphenyl aryl, fused ring aryl, etc. The introduction of the benzene ring structure is beneficial to increasing the refractive index of the thermoplastic resin and also beneficial to increasing the glass transition temperature Tg of the thermoplastic resin.

[0057] In this embodiment, the substituted or unsubstituted polycyclic aryl group may comprise 2 to 10 benzene rings. A suitable number of benzene rings is beneficial for achieving a high refractive index in the resin composition while maintaining the glass transition temperature (Tg) of the thermoplastic resin at a moderate value. This facilitates processing and molding of the thermoplastic resin and improves the thermal stability of the resulting optical articles. In some embodiments, the substituted or unsubstituted polycyclic aryl group may comprise 2, 4, 5, 6, 7, or 10 benzene rings.

[0058] In some embodiments of this application, the substituted or unsubstituted polycyclic aryl group may include substituted or unsubstituted naphthylene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthylene, substituted or unsubstituted pyrene, substituted or unsubstituted tetraphenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted binatylene, substituted or unsubstituted isopropylbenzinylene, substituted or unsubstituted fluorene, substituted or unsubstituted spirofluorene, substituted or unsubstituted diphenylfluorene, substituted or unsubstituted dinaphthylfluorene, substituted or unsubstituted dithionylene, substituted or unsubstituted dithionylene, substituted or unsubstituted spirofluoreneanthylene, or substituted or unsubstituted spirofluorenepentaphenylene.

[0059] In this embodiment, the polycyclic heteroaryl group is a divalent polycyclic aromatic group containing heteroatoms (e.g., O, S), which has multiple (two or more) aromatic rings, at least one of which is an aromatic heterocycle. The introduction of aromatic ring structure is beneficial to increasing the refractive index of thermoplastic resin and also beneficial to increasing the glass transition temperature Tg of thermoplastic resin.

[0060] In this embodiment, the substituted or unsubstituted polycyclic heteroaryl group comprises 2-10 aromatic rings. A suitable number of aromatic rings is beneficial for achieving a high refractive index in the resin composition while maintaining the glass transition temperature (Tg) of the thermoplastic resin at a moderate value. This facilitates processing and molding of the thermoplastic resin and improves the thermal stability of the resulting optical articles. In some embodiments, the substituted or unsubstituted polycyclic heteroaryl group may comprise 2, 4, 5, 6, 7, or 10 aromatic rings.

[0061] In some embodiments of this application, the substituted or unsubstituted polycyclic heteroaryl group may include substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted thieno[3,2-b]thiophene, substituted or unsubstituted group of formula (a), substituted or unsubstituted group of formula (b), and substituted or unsubstituted group of formula (c).

[0062] Ar1 and Ar2 are independently selected from aromatic rings or aromatic heterocycles, and at least one of Ar1 and Ar2 is an aromatic heterocycle; the aromatic ring and aromatic heterocycle can be monocyclic or polycyclic structures, and the polycyclic structure can be a fused ring. Ar1 and Ar2 can be, for example, benzene rings, thiophene rings, furan rings, or pyrrole rings.

[0063] L1 and L2 are selected from O, S, Se, and -N(R) respectively. a )-、-P(R b )-、-P(=O)(R c)-, or -Si(R d )-, R a R b R c R d They are aryl or alkyl, respectively. For example, when L1 is S, formula (b) is spirofluorenethionanthyl; when L1 is O, formula (b) is spirofluoreneoxanthyl. When L2 is S, formula (c) is spirofluorenethionanthyl; when L1 is O, formula (c) is spirofluoreneoxanthyl.

[0064] Indicates the connection site.

[0065] In the embodiments of this application, the substituted or unsubstituted monocyclic heterocyclic group can be a monocyclic alicyclic group or a monocyclic aromatic heterocyclic group, such as a substituted or unsubstituted dioxane group, a substituted or unsubstituted dithiohexane group, a substituted or unsubstituted trioxane group (i.e., trioxane), a substituted or unsubstituted trithiaalkyl group (i.e., trioxane), a substituted or unsubstituted furanyl group, or a substituted or unsubstituted thiophene group.

[0066] In the embodiments of this application, the substituent groups in the substituted polycyclic aryl group, the substituted polycyclic heteroaryl group, the substituted phenylene group, and the substituted monocyclic heterocyclic group include one or more of halogen atoms, hydroxyl groups, cyano groups, amino groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkoxy groups, and phenyl groups.

[0067] In this embodiment, R1 has 8-50 carbon atoms; for example, R1 has 8, 10, 12, 15, 18, 20, 25, 30, 35, 40, 45, or 50 carbon atoms. R2 has 3-50 carbon atoms; for example, R2 has 3, 5, 8, 10, 12, 15, 18, 20, 25, 30, 35, 40, 45, or 50 carbon atoms. Suitable carbon atom numbers allow R1 and R2 to have suitable group sizes.

[0068] In the embodiments of this application, m1 and m2 are independently integers from 0 to 10, for example, m1 and m2 are independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10.

[0069] In some embodiments of this application, R1 comprises a spirocyclic structure. Exemplarily, R1 may be, but is not limited to, substituted or unsubstituted fluoreneyl, substituted or unsubstituted spirodifluoreneyl, substituted or unsubstituted diphenylfluoreneyl, substituted or unsubstituted dinaphthylfluoreneyl, substituted or unsubstituted spirofluorenethixanthyl, substituted or unsubstituted spirofluoreneoxoxanthyl, substituted or unsubstituted spirofluorenethixapentanthyl, or substituted or unsubstituted spirofluoreneoxapentanthyl. The spirocyclic structure comprises multiple aromatic rings, has a large three-dimensional spatial structure, and is highly rigid, which is beneficial for improving the refractive index and glass transition temperature (Tg) of thermoplastic resins.

[0070] In some embodiments of this application, R1 includes a naphthalene ring structure. The introduction of a naphthalene ring structure into the repeating unit can better improve the refractive index of the thermoplastic resin composition while also achieving a higher glass transition temperature and a higher Abbe number.

[0071] In some embodiments of this application, R1 includes a spirocyclic structure or a naphthalenecyclic structure; R2 is a substituted or unsubstituted phenylene, a substituted or unsubstituted polycyclic aryl, a substituted or unsubstituted monocyclic heterocyclic, or a substituted or unsubstituted polycyclic heterocyclic.

[0072] In some embodiments of this application, R2 is a substituted or unsubstituted polycyclic aryl group, or a substituted or unsubstituted polycyclic heteroaryl group. A polycyclic aromatic structure of R2 is beneficial for increasing the refractive index and glass transition temperature (Tg) of the thermoplastic resin.

[0073] In some embodiments of this application, R1 comprises a spirocyclic structure or a naphthalenecyclic structure; and / or, R2 is a substituted or unsubstituted polycyclic aryl group, or a substituted or unsubstituted polycyclic heteroaryl group.

[0074] In some embodiments of this application, R1 comprises a naphthalene ring structure, or R2 comprises a naphthalene ring structure. The introduction of a naphthalene ring structure into the repeating unit can better improve the refractive index of the thermoplastic resin composition while also achieving a higher glass transition temperature and a higher Abbe number.

[0075] In some embodiments of this application, R1 comprises a spirocyclic structure, and either R1 or R2 comprises a naphthalene ring structure. This is advantageous for achieving both a high refractive index and an Abbe number, while simultaneously obtaining a higher glass transition temperature Tg.

[0076] In some embodiments of this application, R1 includes a spirocyclic structure, while R2 is a substituted or unsubstituted polycyclic aryl group or a substituted or unsubstituted polycyclic heteroaryl group.

[0077] In some embodiments of this application, R1 comprises a spirocyclic structure, while R2 comprises a fused ring structure, which is beneficial for better balancing high refractive index, high Abbe number, and high glass transition temperature Tg. In some embodiments of this application, R1 comprises a spirocyclic structure, while R2 comprises a naphthalene ring structure.

[0078] In some embodiments of this application, R1 includes a spirocyclic structure and a naphthalenecyclic structure.

[0079] In some embodiments of this application, R2 contains sulfur atoms. The presence of sulfur atoms in R2 can increase the sulfur content of the thermoplastic resin, thereby better controlling the glass transition temperature Tg of the thermoplastic resin and reducing the decay of the Abbe number.

[0080] In some embodiments of this application, R2 is a substituted or unsubstituted polycyclic aryl group containing a sulfur atom, or a substituted or unsubstituted polycyclic heteroaryl group containing a sulfur atom.

[0081] In some embodiments of this application, R1 includes a spirocyclic structure, while R2 is a substituted or unsubstituted polycyclic aryl group containing a sulfur atom, or a substituted or unsubstituted polycyclic heteroaryl group containing a sulfur atom.

[0082] In some embodiments of this application, R1 comprises a naphthalene ring structure, while R2 is a substituted or unsubstituted polycyclic aryl group containing a sulfur atom, or a substituted or unsubstituted polycyclic heteroaryl group containing a sulfur atom.

[0083] In some embodiments of this application, R1 is a group represented by formula (a);

[0084] Ar1 and Ar2 can be independently selected from aromatic rings or heterocyclic aromatic rings. The linkage site is indicated. Aromatic rings and aromatic heterocycles can be monocyclic or polycyclic structures, and polycyclic structures can be fused rings. Ar1 and Ar2 can be, for example, but are not limited to, benzene rings, thiophene rings, furan rings, and pyrrole rings. When both Ar1 and Ar2 are aromatic rings, the group shown in formula (a) is a polycyclic aryl group, for example. When one or both of Ar1 and Ar2 are aromatic heterocycles, the group shown in formula (a) is a polycyclic heteroaryl group.

[0085] In some embodiments of this application, R1 is a group represented by formula (a), and R2 contains a sulfur atom.

[0086] In some embodiments of this application, R1 is a group represented by formula (a), and R2 is a substituted or unsubstituted polycyclic aryl group or a substituted or unsubstituted polycyclic heteroaryl group.

[0087] In this embodiment, the sulfur content in the thermoplastic resin is greater than or equal to 8% by mass. Increasing the sulfur content in the thermoplastic resin is beneficial for improving the refractive index. However, increasing the sulfur content also lowers the glass transition temperature (Tg) of the thermoplastic resin. To better balance refractive index and glass transition temperature (Tg), in some embodiments, the sulfur content in the thermoplastic resin is greater than or equal to 8% and less than or equal to 20% by mass; in some embodiments, the sulfur content is greater than or equal to 8% and less than or equal to 17% by mass. In some embodiments, the sulfur content in the thermoplastic resin is 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, or 17% by mass.

[0088] The thermoplastic resin composition of this application embodiment, through the comprehensive regulation of the structure of each part in the repeating unit shown in formula (1), can have a high refractive index, a high Abbe number and a suitable glass transition temperature Tg, and can be prepared by reaction at room temperature, and can be compatible with existing injection molding processes.

[0089] In the embodiments of this application, R1 consists of a substituted or unsubstituted polycyclic aryl group, which is directly connected to an O atom via an aromatic carbon atom; R2 consists of a substituted or unsubstituted phenylene group, which is directly connected to an S atom via an aromatic carbon atom. The aromatic carbon atom is a carbon atom that constitutes an aromatic ring.

[0090] In some embodiments of this application, R1 is a substituted or unsubstituted polycyclic arylene, and R2 is a substituted or unsubstituted phenylene, a substituted or unsubstituted polycyclic arylene, a substituted or unsubstituted monocyclic heterocyclic group, or a substituted or unsubstituted polycyclic heterocyclic group.

[0091] In other embodiments of this application, R1 is a substituted or unsubstituted polycyclic heterocyclic aryl group, and R2 is a substituted or unsubstituted phenylene, a substituted or unsubstituted polycyclic aryl group, a substituted or unsubstituted monocyclic heterocyclic aryl group, or a substituted or unsubstituted polycyclic heterocyclic aryl group.

[0092] In some embodiments of this application, the repeating unit shown in equation (1) is as shown in equations (1-1) to (1-8):

[0093] Formula (1-1) corresponds to R1 being diphenylfluoreneyl and R2 being naphthylene;

[0094] Formula (1-2) corresponds to R1 being a naphthylene, R2 being a dithionylhexane, and m1 and m2 are both 1;

[0095] Formula (1-3) corresponds to R1 being a naphthylene and R2 being a diphenylthionine;

[0096] Formula (1-4) corresponds to R1 being dinaphthylfluorene group, R2 being dithionylhexane group, and m1 and m2 are both 1;

[0097] Formula (1-5) corresponds to R1 being dinaphthylfluorenyl and R2 being dithionyldiphenyl;

[0098] Formula (1-6) corresponds to R1 being dinaphthylfluorene and R2 being phenylene;

[0099] Formula (1-7) corresponds to R1 being isopropylidene dinaphthyl and R2 being dithionide diphenyl;

[0100] Formula (1-8) corresponds to R1 being a naphthylene and R2 being a phenylene.

[0101] In this application, the weight-average molecular weight (Mw) of the thermoplastic resin is 2,000-100,000 (Da). In some embodiments, the weight-average molecular weight of the thermoplastic resin is 2,000, 5,000, 10,000, 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, or 100,000. The weight-average molecular weight (Mw) of the thermoplastic resin can be obtained by gel permeation chromatography (GPC).

[0102] In this embodiment, the molecular weight distribution index (PDI) of the thermoplastic resin is less than or equal to 1.6. The molecular weight distribution index (PDI) is a parameter used to represent the width of the molecular weight distribution. It is usually calculated as the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn). A higher PDI value indicates a wider molecular weight distribution, meaning higher molecular weight inhomogeneity; a lower PDI value indicates a narrower molecular weight distribution, meaning higher molecular weight uniformity. A lower PDI in thermoplastic resins is beneficial for improving their film-forming properties, obtaining more uniform resin films, and improving the performance of optical products. A lower PDI also facilitates better flowability, thereby enabling better control of the processing process and reducing processing costs and difficulty. In some embodiments, the molecular weight distribution index (PDI) of the thermoplastic resin is 1.0-1.6, for example, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, and 1.6. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of thermoplastic resins can be obtained by gel permeation chromatography (GPC), and then the molecular weight distribution index (PDI) of thermoplastic resins can be calculated.

[0103] In this embodiment, the refractive index of the thermoplastic resin is greater than or equal to 1.66. The refractive index of the thermoplastic resin is the ratio of the speed of light in a vacuum to the speed of light in the thermoplastic resin, and can be represented by n. The higher the refractive index of the material, the stronger its ability to refract incident light. Thermoplastic resin has a high refractive index, which is beneficial to improving the refractive ability of the optical lenses made from it. This helps to improve the sharpness of photographs for camera lenses and improve the clarity of vision for eyeglass lenses. In addition, the high refractive index of thermoplastic resin can further reduce the thickness of optical lenses. In some embodiments, the refractive index of the thermoplastic resin is 1.67, 1.68, 1.69, 1.70, or 1.71. The refractive index of the thermoplastic resin can be measured using an Abbe refractometer, an ellipsometer, or a prism coupler.

[0104] In this embodiment, the Abbe number of the thermoplastic resin is greater than or equal to 15. The Abbe number is a physical quantity used to measure the degree of dispersion of a transparent medium. The higher the Abbe number, the smaller the dispersion, and the clearer the visual effect of the optical lens made from the thermoplastic resin; conversely, the lower the Abbe number, the more severe the dispersion. In some embodiments, the Abbe number of the thermoplastic resin is greater than or equal to 16. In some embodiments, the Abbe number of the thermoplastic resin is greater than or equal to 18. In some embodiments, the Abbe number of the thermoplastic resin is greater than or equal to 19. In some embodiments, the Abbe number of the thermoplastic resin is greater than or equal to 20. In some embodiments, the Abbe number of the thermoplastic resin is greater than or equal to 22. In some embodiments, the Abbe number of the thermoplastic resin is greater than or equal to 25. The Abbe number of the thermoplastic resin can be measured using an Abbe refractometer, an ellipsometer, or a prism coupler.

[0105] In this application, the glass transition temperature (Tg) of the thermoplastic resin is greater than or equal to 40°C. In some embodiments of this application, the glass transition temperature (Tg) of the thermoplastic resin is greater than or equal to 80°C. The glass transition temperature (Tg) refers to the temperature at which the thermoplastic resin transitions from a glassy state to a rubbery state. The glass transition temperature can be determined using methods such as differential scanning calorimetry (DSC), dynamic mechanical property analysis (DMA), and thermomechanical methods. A relatively high glass transition temperature (Tg) of the thermoplastic resin is beneficial for improving the service reliability of the resulting optical products; while a relatively low glass transition temperature (Tg) is beneficial for manufacturing optical products at lower processing temperatures. In some embodiments, the glass transition temperature (Tg) of the thermoplastic resin is less than 160°C. In some embodiments, the glass transition temperature (Tg) of the thermoplastic resin is 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 153°C, or 155°C.

[0106] In the embodiments of this application, the thermal decomposition temperature Td of the thermoplastic resin (10％)The thermal decomposition temperature (Td) is greater than or equal to 320℃. Td refers to the temperature at which the thermoplastic resin begins to decompose; a higher thermal decomposition temperature indicates better heat resistance. (10％) This refers to the temperature at which a thermoplastic resin loses 10% of its weight due to heat. In some embodiments, the thermal decomposition temperature Td of the thermoplastic resin is... (10％) Greater than or equal to 330°C. In some embodiments, the thermal decomposition temperature Td of the thermoplastic resin is... (10％) Greater than or equal to 340°C. In some embodiments, the thermal decomposition temperature Td of the thermoplastic resin is... (10％) Greater than or equal to 350°C. In some embodiments, the thermal decomposition temperature Td of the thermoplastic resin is... (10％) 360℃ or higher.

[0107] This application also provides a method for preparing the above-mentioned thermoplastic resin, comprising:

[0108] The diol acrylate monomer shown in formula (2) and the dithiol monomer shown in formula (3) are dissolved in an organic solvent, and a click reaction is carried out under a protective atmosphere, with the aid of an initiator and at room temperature to obtain a thermoplastic resin. The thermoplastic resin includes the repeating unit shown in formula (1).

[0109] In formulas (1) and (2), R1 is a substituted or unsubstituted polycyclic aryl group or a substituted or unsubstituted polycyclic heteroaryl group;

[0110] In formulas (1) and (3), R2 is a substituted or unsubstituted phenylene, a substituted or unsubstituted polycyclic aryl group, a substituted or unsubstituted monocyclic heterocyclic group, or a substituted or unsubstituted polycyclic heterocyclic group; m1 and m2 are independent integers from 0 to 10.

[0111] The specific choices of R1 in equation (2) and R2 in equation (3) are as described above.

[0112] In this embodiment of the application, the protective atmosphere may be a nitrogen atmosphere or an argon atmosphere.

[0113] In this embodiment, the initiator may be triethylamine or an ionic liquid. The ionic liquid may be one or more of the following:

[0114] In the embodiments of this application, the organic solvent may be one or more of tetrahydrofuran (THF), dichloromethane (DCM), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO).

[0115] The ambient temperature can be between 10℃ and 30℃, for example, 10℃, 20℃, 25℃, and 30℃. The reaction time can be between 1 and 4 hours, for example, 1 hour, 2 hours, 3 hours, and 4 hours.

[0116] The above-mentioned click reaction can be monitored using thin-layer chromatography (TLC) to determine whether the reaction is complete. A mixture of ethyl acetate and petroleum ether can be used as the developing solvent for TLC spotting, for example, a 1:1 mass ratio of ethyl acetate and petroleum ether.

[0117] In this embodiment, after the reaction is complete, the thermoplastic resin dissolves in tetrahydrofuran. A solvent-replacement crystallization method can be used to precipitate the thermoplastic resin into a solid. After filtration and washing to remove the solvent, the thermoplastic resin is obtained. The solvent-replacement crystallization method for precipitating the thermoplastic resin into a solid may include: adding petroleum ether to the reaction system to precipitate the thermoplastic resin into a solid. Washing may be performed using petroleum ether and methanol.

[0118] The method for preparing thermoplastic resin provided in this application embodiment can react at room temperature without the need for water and oxygen control. The preparation process is simple, can be synthesized quickly, and can be operated at room temperature throughout, making the method highly safe.

[0119] This application also provides a resin composition comprising the above-described thermoplastic resin or the thermoplastic resin prepared by the above-described preparation method. The resin composition is a thermoplastic resin composition.

[0120] In this embodiment, the resin composition may include other additives in addition to the thermoplastic resin of the embodiments of this application. For example, the resin composition may also include one or more additives selected from fillers, dyes, antioxidants, anti-yellowing agents, light stabilizers, ultraviolet absorbers, plasticizers, flame retardants, antistatic agents, and release agents. The above-mentioned additives may be added according to actual functional requirements. In some embodiments, the resin composition may also include other thermoplastic resins.

[0121] In the embodiments of this application, the above-mentioned thermoplastic resin or resin composition can be processed into optical products by various known molding methods, such as injection molding; other methods include injection molding, extrusion molding, solution casting, foaming molding, blow molding, compression molding, calendering, rotational molding, etc. The thermoplastic resin of the embodiments of this application is compatible with existing injection molding processes, reducing processing difficulty and facilitating industrial applications.

[0122] This application also provides an optical article comprising a molded article of the aforementioned thermoplastic resin, or a molded article comprising the aforementioned resin composition. The optical article may be partially or wholly composed of a molded article of the aforementioned thermoplastic resin, or a molded article of the aforementioned resin composition.

[0123] In this application, the optical product may include an optical lens, an optical film, an optical disc, a light guide plate, or a display panel.

[0124] Optical lenses can include eyeglass lenses, camera lenses, sensor lenses, illumination lenses, imaging lenses, or lidar lenses. Eyeglass lenses can include lenses for nearsightedness, reading glasses, sunglasses, corrective contact lenses, and goggles. Camera lenses are commonly used in camera modules of devices, specifically in mobile phone cameras, laptop cameras, desktop cameras, and automotive cameras. Sensor lenses can be motion detector lenses, proximity sensor lenses, attitude control lenses, and infrared sensor lenses. Illumination lenses can be indoor lighting lenses, outdoor lighting lenses, vehicle headlight lenses, vehicle fog light lenses, vehicle rearlight lenses, vehicle daytime running light lenses, vehicle fog light lenses, vehicle interior lenses, light-emitting diode (LED) lenses, or organic light-emitting diode (OLED) lenses. Imaging lenses can be AR / VR lenses, scanner lenses, projector lenses, telescope lenses, microscope lenses, and magnifying glass lenses.

[0125] Exemplary optical films may include light guide films, reflective films, antireflective films, diffusion films, light filter films, polarizing films, beam splitting films, and phase films, etc. Optical films can be used in display fields, lighting fields, etc., for example, they can be used as films for liquid crystal substrates.

[0126] This application also provides a device, which includes a carrier and the aforementioned optical article mounted on the carrier. The device may be a mobile terminal, glasses, a camera (such as a camera), a sensing device, a lighting device (such as a desk lamp, ceiling light, street light, etc.), an imaging device (such as an AR / VR imaging device, microscope, telescope, projector, scanner, etc.), a lidar, etc.

[0127] Mobile terminals can specifically include various handheld devices with wireless communication functions (such as mobile phones, tablets, mobile laptops, netbooks), wearable devices (such as smartwatches), or other processing devices connected to a wireless modem, as well as various forms of user equipment (UE), mobile station (MS), terminal device, etc.

[0128] In some embodiments of this application, the mobile terminal includes a device body and a camera module mounted on the device body. The device body includes a carrier, and the camera module includes a lens. The lens is made of the thermoplastic resin or the resin composition described above.

[0129] The technical solution of this application will be further described below with reference to several embodiments:

[0130] Example 1

[0131] The preparation of thermoplastic resin P1 includes the following steps:

[0132] (1) At room temperature, 10 mL of dichloromethane (DCM) was added to bisphenol fluorene (0.5 g, 1.43 mmol, 1 eq.), followed by the dropwise addition of triethylamine (0.288 g, 2.86 mmol, 2.2 eq.) and acryloyl chloride (0.279 g, 3.14 mmol, 2.2 eq.). The mixture was stirred at room temperature for 3 hours under nitrogen protection. After confirming that the reaction of the raw materials was basically complete by TLC (using a mixture of ethyl acetate and petroleum ether at a mass ratio of 1:4 as the developing solvent), 200 mL of ethyl acetate (EA) was added for extraction 4 times. The organic phases were combined, dried over anhydrous sodium sulfate, concentrated under reduced pressure to dryness, and passed through a fast column to obtain 582 mg of white solid product, which was the glycol acrylate monomer A1, with a yield of 89%.

[0133] (2) Dissolve the glycol acrylate monomer A1 obtained in step (1) in 10 mL of tetrahydrofuran (THF), add triethylamine and dithiol monomer B1, and react at room temperature for 3 hours. After confirming that the monomer reaction is basically complete by TLC (using a mixture of ethyl acetate and petroleum ether in a mass ratio of 1:1 as the developing solvent), add 20 mL of petroleum ether, and a white solid precipitates. Filter the solid product and wash it with 3 × 20 mL of petroleum ether and 1 × 5 mL of methanol. Then collect the solid and remove liquid impurities such as solvents using a vacuum oil pump to obtain thermoplastic resin P1.

[0134] The above reaction process is shown in the following equation:

[0135] The Tg of thermoplastic resin P1 was determined to be 151.54℃ using DSC (Differential Scanning Calorimetry). The Td of thermoplastic resin P1 was determined using TGA (Thermogravimetric Analysis). (10％)=361.47℃. Figure 1 is the 1H NMR spectrum of the thermoplastic resin P1 prepared in Example 1 of this application. 1H NMR (300MHz, CDCl3) δ 8.42-8.39 (m, 2H), 7.73-7.67 (m, 4H), 7.48-7.44 (m, 2H), 7.34-7.29 (m, 4H), 7.24-7.21 (m, 2H), 7.17-7.15 (m, 2H), 6.90-6.88 (m, 4H), 3.26-3.22 (t, 4H), 2.78-2.76 (t, 4H)). The Mn = 45611 Da, Mw = 70911 Da, and PDI = Mw / Mn = 1.55 of the thermoplastic resin P1 were obtained by GPC (Gel Permeation Chromatography).

[0136] Example 2

[0137] The preparation of thermoplastic resin P2 includes the following steps:

[0138] (1) At room temperature, 20 mL of dichloromethane (DCM) was added to binaphthol (2 g, 6.99 mmol, 1 eq.), followed by the dropwise addition of triethylamine (1.554 g, 15.4 mmol, 2.2 eq.) and acryloyl chloride (1.371 g, 15.4 mmol, 2.2 eq.). The mixture was stirred at room temperature for 3 hours under nitrogen protection. After confirming that the reaction of the raw materials was basically complete by TLC (using a mixture of ethyl acetate and petroleum ether at a mass ratio of 1:4 as the developing solvent), 200 mL of ethyl acetate (EA) was added for extraction four times. The organic phases were combined, dried over anhydrous sodium sulfate, concentrated to dryness under reduced pressure, and passed through a fast column to obtain 1.088 g of white solid product, which was glycol acrylate monomer A2, with a yield of 79%.

[0139] (2) Dissolve the diol acrylate monomer A2 obtained in step (1) in 10 mL of tetrahydrofuran (THF), add triethylamine and dithiol monomer B2, and react at room temperature for 3 hours. After confirming that the monomer reaction is basically complete by TLC (using a mixture of ethyl acetate and petroleum ether with a mass ratio of 1:1 as the developing solvent), add 20 mL of petroleum ether, and a white solid precipitates. Filter the solid product and wash it with 3 × 20 mL of petroleum ether and 1 × 5 mL of methanol. Then collect the solid and remove liquid impurities such as solvents using a vacuum oil pump to obtain thermoplastic resin P2.

[0140] The above reaction process is shown in the following equation:

[0141] The Tg of thermoplastic resin P2 was determined to be 42.91℃ using DSC (Differential Scanning Calorimetry). The Td (10%) of thermoplastic resin P2 was determined to be 327.95℃ using TGA (Thermogravimetric Analysis). Figure 2 shows the 1H NMR spectrum of thermoplastic resin P2 prepared in Example 2 of this application. 1H NMR (300MHz, CDCl3) δ 8.02-7.98 (m, 2H), 7.95-7.93 (m, 2H), 7.48-7.42 (m, 4H), 7.35-7.28 (m, 2H), 7.21-7.19 (m, 2H), 3.11-2.19 (m, 18H). The thermoplastic resin P2 was tested using GPC (Gel Permeation Chromatography) and found to have Mn = 3093 Da, Mw = 3682 Da, and PDI = Mw / Mn = 1.19.

[0142] Example 3

[0143] The preparation of thermoplastic resin P3 includes the following steps:

[0144] Diol acrylate monomer A2 was dissolved in 10 mL of tetrahydrofuran (THF), and triethylamine and dithiol monomer B3 were added. The mixture was reacted at room temperature for 3 hours. After confirming that the monomers had basically reacted completely by TLC (using a 1:1 mass ratio mixture of ethyl acetate and petroleum ether as the developing solvent), 20 mL of petroleum ether was added, and a white solid precipitated. The solid product was filtered and washed with 3 × 20 mL of petroleum ether and 1 × 5 mL of methanol. The solid was then collected, and liquid impurities such as solvents were removed using a vacuum oil pump to obtain thermoplastic resin P3.

[0145] The above reaction process is shown in the following equation:

[0146] The Tg of thermoplastic resin P3 was determined to be 86.23℃ using DSC (Differential Scanning Calorimetry). The Td (10%) of thermoplastic resin P3 was determined to be 352.73℃ using TGA (Thermogravimetric Analysis). Figure 3 shows the 1H NMR spectrum of thermoplastic resin P3 prepared in Example 3 of this application. 1H NMR (300MHz, CDCl3) δ 7.93-7.85 (m, 4H), 7.45-7.36 (m, 4H), 7.19-7.13 (, 7H), 7.03-6.96 (, 4H), 2.67-2.53 (m, 4H), 2.39-2.31 (m, 4H). The thermoplastic resin P3 was tested using GPC (Gel Permeation Chromatography) and found to have Mn = 13692 Da, Mw = 17117 Da, and PDI = Mw / Mn = 1.25.

[0147] Example 4

[0148] The preparation of thermoplastic resin P4 includes the following steps:

[0149] (1) 9-fluorenone (1.8 g, 2.13 mmol, 1 eq.), 2-naphthol (3.31 g, 2.5 eq.), 3-mercaptopropionic acid (0.1 g, 0.05 eq.), and concentrated sulfuric acid (2 g, 2 eq.) were added sequentially to a 100 mL sealed tube; the mixture was stirred and heated to 100 °C and stirred for 2 h; the reaction solution was diluted with 10 mL of EA and neutralized to neutral with 10 wt% NaOH aqueous solution. The mixture was extracted twice with EA, the organic phases were combined, dried, and concentrated to dryness under reduced pressure; column chromatography was performed, and the sample was loaded by dry method. The column was PE:EA = 5:1 with a single polarity to obtain a pale yellow bubbly solid BNF;

[0150] (2) BNF (2g, 4.44mmol, 1eq.) was added to 20mL of DCM at room temperature, followed by the dropwise addition of triethylamine (1.347g, 13.3mmol, 3eq.) and acryloyl chloride (0.870g, 9.78mmol, 2.2eq.). The mixture was stirred at room temperature under nitrogen for 3 hours. After confirming that the reaction of the raw materials was basically complete by TLC (using a mixture of ethyl acetate and petroleum ether at a mass ratio of 1:4 as the developing solvent), 200mL of ethyl acetate (EA) was added for extraction four times. The organic phases were combined, dried over anhydrous sodium sulfate, concentrated under reduced pressure to dryness, and passed through a fast column to obtain 1.90g of brown solid product, which was the glycol acrylate monomer A3, with a yield of 77%.

[0151] (3) Dissolve the diol acrylate monomer A3 obtained in step (2) in 10 mL of tetrahydrofuran (THF), add triethylamine and dithiol monomer B2, and react at room temperature for 3 hours. After confirming that the monomer reaction is basically complete by TLC (using a mixture of ethyl acetate and petroleum ether with a mass ratio of 1:1 as the developing solvent), add 20 mL of petroleum ether, and a white solid precipitates. Filter the solid product and wash it with 3 × 20 mL of petroleum ether and 1 × 5 mL of methanol. Then collect the solid and remove liquid impurities such as solvents using a vacuum oil pump to obtain thermoplastic resin P4.

[0152] The above reaction process is shown in the following equation:

[0153] The Tg of thermoplastic resin P4 was determined to be 97.49℃ using DSC (Differential Scanning Calorimetry). The Td (10%) of thermoplastic resin P4 was determined to be 323.36℃ using TGA (Thermogravimetric Analysis). Figure 4 shows the 1H NMR spectrum of thermoplastic resin P4 prepared in Example 4 of this application. ¹H NMR (300MHz, CDCl₃) δ 7.82–7.80 (m, 2H), 7.74–7.59 (m, 4H), 7.49–7.46 (m, 3H), 7.42–7.37 (m, 3H), 7.29–7.27 (m, 1H), 7.16–7.13 (m, 1H), 3.75–3.72 (m, 2H), 3.11–2.84 (m, 14H), 1.85–1.80 (m, 2H). GPC (Gel Permeation Chromatography) analysis yielded Mn = 5363 Da, Mw = 7089 Da, and PDI = Mw / Mn = 1.32 for thermoplastic resin P4.

[0154] Example 5

[0155] The preparation of thermoplastic resin P5 includes the following steps:

[0156] The glycol acrylate monomer A3, as shown below, was dissolved in 10 mL of tetrahydrofuran (THF). Triethylamine and dithiol monomer B3 were added, and the mixture was reacted at room temperature for 3 hours. After confirming that the monomers had basically reacted completely by TLC (using a 1:1 mass ratio mixture of ethyl acetate and petroleum ether as the developing solvent), 20 mL of petroleum ether was added, and a white solid precipitated. The solid product was filtered and washed with 3 × 20 mL of petroleum ether and 1 × 5 mL of methanol. The solid was then collected, and liquid impurities such as solvents were removed using a vacuum oil pump to obtain thermoplastic resin P5.

[0157] The above reaction process is shown in the following equation:

[0158] The Tg of thermoplastic resin P5 was determined to be 145.19℃ using DSC (Differential Scanning Calorimetry). The Td (10%) of thermoplastic resin P5 was determined to be 349.40℃ using TGA (Thermogravimetric Analysis). Figure 5 shows the 1H NMR spectrum of thermoplastic resin P5 prepared in Example 5 of this application. 1H NMR (300MHz, CDCl3) δ 7.81-7.79 (m, 2H), 7.68-7.58 (m, 6H), 7.47-7.23 (m, 14H), 7.12-7.09 (m, 7H), 3.27-323 (t, 4H), 2.89-2.86 (t, 4H) The thermoplastic resin P5 was tested using GPC (Gel Permeation Chromatography) and found to have Mn = 18192 Da, Mw = 28249 Da, and PDI = Mw / Mn = 1.55.

[0159] The refractive index n, Abbe number Vd, and molecular weight M of the thermoplastic resins of Examples 1 to 5 and the commercial Mitsubishi EP9000 optical resin of Comparative Example 1 were compared. w Molecular weight M n The test results for glass transition temperature (Tg), thermal decomposition temperature (Td), and sulfur content are listed in Table 1. The refractive index and Abbe number were obtained by hot-pressing the resin into 70 μm thick samples and measuring them using an Abbe refractometer. Table 1 lists the refractive indices of the resin under incident light of 486 nm, 589 nm, and 656 nm. The sulfur content was obtained through elemental analysis.

[0160] Table 1

[0161] As can be seen from the results in Table 1, compared with the existing commercial optical resin of Comparative Example 1, the thermoplastic resin of this application embodiment has an improved refractive index, a relatively high Abbe number, and a suitable glass transition temperature.

[0162] It should be understood that the use of the terms "first," "second," and various numerical designations in this document is merely for descriptive convenience and is not intended to limit the scope of this application.

[0163] In this application, "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone, where A and B can be singular or plural. The character " / " generally indicates that the related objects before and after it are in an "or" relationship.

[0164] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0165] In this application, "-" indicates a range value, including the endpoint values ​​at both ends. For example, the value of a can be 0.5-15, meaning that the value of a can be between 0.5 and 15, and includes the endpoint values ​​of 0.5 and 15.

[0166] It should be understood that in the various embodiments of this application, the order of the above processes does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.

Claims

1. A thermoplastic resin, characterized in that, The thermoplastic resin comprises repeating units as shown in formula (1). In formula (1), R1 is a substituted or unsubstituted polycyclic arylene or a substituted or unsubstituted polycyclic heteroarylene, R2 is a substituted or unsubstituted phenylene, a substituted or unsubstituted polycyclic arylene, a substituted or unsubstituted monocyclic heterocyclic group or a substituted or unsubstituted polycyclic heteroarylene; m1 and m2 are independent integers from 0 to 10.

2. The thermoplastic resin according to claim 1, characterized in that, The substituted or unsubstituted polycyclic aromatic hydrocarbons comprise 2-10 benzene rings; the substituted or unsubstituted polycyclic heteroaryl hydrocarbons comprise 2-10 aromatic rings.

3. The thermoplastic resin as described in claim 1 or 2, characterized in that, The substituted or unsubstituted polycyclic aryl groups include substituted or unsubstituted naphthylene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthylene, substituted or unsubstituted pyrene, substituted or unsubstituted tetraphenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted binatylene, substituted or unsubstituted isopropylbenzinylene, substituted or unsubstituted fluorene, substituted or unsubstituted spirofluorene, substituted or unsubstituted diphenylfluorene, substituted or unsubstituted dinaphthylfluorene, substituted or unsubstituted dithionylbenzylene, substituted or unsubstituted dithionylbenzylene, substituted or unsubstituted spirofluoreneanthryl, or substituted or unsubstituted spirofluorenepentaphenylene.

4. The thermoplastic resin according to any one of claims 1-3, characterized in that, The substituted or unsubstituted polycyclic heteroaryl groups include substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted thieno[3,2-b]thienophene, substituted or unsubstituted groups of formula (a), substituted or unsubstituted groups of formula (b), and substituted or unsubstituted groups of formula (c). Ar1 and Ar2 are independently selected from aromatic rings or aromatic heterocyclic rings, and at least one of Ar1 and Ar2 is an aromatic heterocyclic ring; L1 and L2 are selected from O, S, Se, and -N(R) respectively. a )-、-P(R b )-、-P(=O)(R c )-, or -Si(R d )-, R a R b R c R d They are aryl or alkyl, respectively; Indicates the connection site.

5. The thermoplastic resin according to any one of claims 1-4, characterized in that, The substituted or unsubstituted monocyclic heterocyclic groups include substituted or unsubstituted dioxane, substituted or unsubstituted dithiohexane, substituted or unsubstituted trioxane, substituted or unsubstituted trithiaalkyl, substituted or unsubstituted furanyl, or substituted or unsubstituted thiopheneyl.

6. The thermoplastic resin according to any one of claims 1-5, characterized in that, The substituted polycyclic aryl group, substituted polycyclic heteroaryl group, substituted phenylene group, and substituted monocyclic heterocyclic group include one or more of halogen atoms, hydroxyl groups, cyano groups, amino groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkoxy groups, and phenyl groups.

7. The thermoplastic resin according to any one of claims 1-6, characterized in that, R1 comprises a spirocyclic structure or a naphthalenecyclic structure; and / or, R2 is a substituted or unsubstituted polycyclic aryl group or a substituted or unsubstituted polycyclic heteroaryl group.

8. The thermoplastic resin according to any one of claims 1-7, characterized in that, The R2 contains sulfur atoms.

9. The thermoplastic resin according to any one of claims 1-8, characterized in that, R1 includes a naphthalene ring structure, or R2 includes a naphthalene ring structure.

10. The thermoplastic resin according to any one of claims 1-9, characterized in that, R1 includes a naphthalene ring structure or R2 includes a naphthalene ring structure, and R1 includes a spiro ring structure.

11. The thermoplastic resin according to any one of claims 1-10, characterized in that, The R1 includes the group shown in formula (a); Ar1 and Ar2 can be independently selected from aromatic rings or heterocyclic aromatic rings. Indicates the connection site.

12. The thermoplastic resin according to any one of claims 1-11, characterized in that, In R1, the substituted or unsubstituted polycyclic aryl group is directly connected to the O atom through the aromatic carbon nucleus; In R2, the substituted or unsubstituted phenylene, the substituted or unsubstituted polycyclic aryl group, and the substituted or unsubstituted polycyclic heteroaryl group are directly connected to the S atom through the aromatic nucleus carbon.

13. The thermoplastic resin according to any one of claims 1-12, characterized in that, The number of carbon atoms in R1 is 8-50; the number of carbon atoms in R2 is 3-50.

14. The thermoplastic resin according to any one of claims 1-13, characterized in that, The repeating unit shown in equation (1) includes any one or more of the structures shown in equations (1-1) to (1-8):

15. The thermoplastic resin according to any one of claims 1-14, characterized in that, The weight-average molecular weight of the thermoplastic resin is 2,000-100,000.

16. The thermoplastic resin according to any one of claims 1-15, characterized in that, The molecular weight distribution index (PDI) of the thermoplastic resin is less than or equal to 1.

6.

17. The thermoplastic resin according to any one of claims 1-16, characterized in that, The thermoplastic resin has a refractive index greater than or equal to 1.

66.

18. The thermoplastic resin according to any one of claims 1-17, characterized in that, The thermoplastic resin has an Abbe number greater than or equal to 15.

19. The thermoplastic resin according to any one of claims 1-18, characterized in that, The glass transition temperature (Tg) of the thermoplastic resin is greater than or equal to 80°C.

20. A method for preparing a thermoplastic resin, characterized in that, include: The diol acrylate monomer shown in formula (2) and the dithiol monomer shown in formula (3) are dissolved in an organic solvent, and a click reaction is carried out under a protective atmosphere, with the aid of an initiator and at room temperature to obtain a thermoplastic resin. The thermoplastic resin includes the repeating unit shown in formula (1). In formulas (1) and (2), R1 is a substituted or unsubstituted polycyclic aryl group or a substituted or unsubstituted polycyclic heteroaryl group; In formulas (1) and (3), R2 is a substituted or unsubstituted phenylene, a substituted or unsubstituted polycyclic aryl group, a substituted or unsubstituted monocyclic heterocyclic group, or a substituted or unsubstituted polycyclic heterocyclic group; m1 and m2 are independent integers from 0 to 10.

21. The method for preparing the thermoplastic resin according to claim 20, characterized in that, The initiator includes triethylamine or an ionic liquid.

22. The method for preparing the thermoplastic resin according to claim 20, characterized in that, The organic solvent includes one or more of tetrahydrofuran, dichloromethane, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide.

23. A resin composition, characterized in that, The resin composition comprises a thermoplastic resin as described in any one of claims 1-19 or a thermoplastic resin prepared by the method described in any one of claims 20-22, and includes additives.

24. The resin composition according to claim 23, characterized in that, The additives include one or more of the following: fillers, dyes, antioxidants, anti-yellowing agents, light stabilizers, ultraviolet absorbers, plasticizers, flame retardants, antistatic agents, and release agents.

25. An optical article, characterized in that, The optical article comprises a molded article of a thermoplastic resin as described in any one of claims 1-19, or a molded article comprising a resin composition as described in claim 23 or 24.

26. The optical article according to claim 25, characterized in that, The optical products include optical lenses, optical films, optical discs, light guide plates, or display panels.

27. The optical article according to claim 26, characterized in that, The optical lenses include eyeglass lenses, camera lenses, sensor lenses, illumination lenses, imaging lenses, or lidar lenses.

28. A device, characterized in that, The device includes a support portion and an optical article as described in any one of claims 25-27, mounted on the support portion.

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