Polymer resin as well as preparation method and application thereof

Abstract

The invention discloses a polymer resin and a preparation method and application thereof, the polymer resin has the following structural general formula as shown in the formula I: # imgabs0 #, and n is a positive integer between 1 and 10000; r1 is a group capable of providing hydrogen atoms, and R2 is an aromatic group or a substituted aromatic group. The polymer resin provided by the invention has more groups and atoms with high refractive index; multiple hydrogen-bond interactions with different strengths are generated among a plurality of hydrogen-bond acceptors and hydrogen-bond donors contained in molecules, so that the intermolecular acting force in the polymer resin is enhanced, and the refractive index of the whole polymer resin is further improved and is higher than 1.8. The aromatic group has certain rigidity, and the thioether bond has certain flexibility, so that the structural toughness and machinability of the whole molecule can be improved.

Description

Technical Field

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

[0002] Optical materials are mainly divided into two categories: glass and resin, and are widely used in multiple fields such as displays, lenses, sensors, etc. Among them, optical resin materials are receiving increasing attention in the field of optical materials.

[0003] Existing optical resin materials, such as polycarbonate resin materials, resin materials formed by curing isocyanate groups-thiols, etc., have a low refractive index, not exceeding 1.7, resulting in a relatively thick thickness, high cost, and poor light efficiency of the optical devices made therefrom. There are also some optical resin materials, such as modified polyphenylene sulfide, which have a complex synthesis process and poor toughness as a resin, and thus are difficult to process, limiting the application of this material in the optical field. Summary of the Invention

[0004] In view of this, the present invention provides a polymeric resin, a preparation method thereof, and an application thereof, aiming to at least solve one of the foregoing technical problems and achieve a high refractive index, good toughness, and processability of the polymeric resin.

[0005] The polymeric resin provided in the first aspect of the present invention has the following general structural formula as shown in Formula I:

[0006]

[0007] Wherein, n is a positive integer between 1 and 10,000; R 1 is a group capable of providing a hydrogen atom, and R 2 is an aromatic group or a substituted aromatic group.

[0008] As can be seen from the above technical solutions, the polymeric resin proposed in the first aspect of the present invention has a triazine group in its monomer. The refractive index of the triazine group is higher than 1.5, providing a structural basis for high refractive index for the entire polymeric resin. Moreover, the monomer has S both on the main chain and the side chain, and S has a relatively high proportion in the whole molecule. S itself is a group with a high molar refractive index, and the propagation speed of light slows down when passing through it, increasing the refractive index. The molecule contains abundant hydrogen bond acceptors including sulfur ether, nitrogen atoms in the triazine group, and sulfur atoms with lone pairs of electrons on its side chain. The molecule also contains abundant hydrogen bond donors such as groups that can provide hydrogen atoms on the side chain of the triazine group. Hydrogen bonds are generated between the hydrogen bond acceptors and hydrogen bond donors, forming multiple and unequal-strength hydrogen bond interactions in the whole molecule, enhancing the intermolecular force in the polymeric resin, achieving the effect of dense packing, and thus further increasing the refractive index of the entire polymeric resin. The main chain in the molecule of the present invention is a triazine group with a certain rigidity, an aromatic group with a certain rigidity or a substituted aromatic group, and a sulfur ether bond with a certain flexibility, making the molecule have a certain rigidity while maintaining a low chain freedom degree, and making the molecular weight of the whole molecule relatively large, which is beneficial to improving the structural toughness and processability of the whole molecule.

[0009] In some possible embodiments of the present invention, R 1 includes an alkyl group with a carbon atom number less than or equal to 4 or a hydroxyphenyl group.

[0010] In some possible embodiments of the present invention, R 2 includes a phenyl group, a diphenyl sulfide group, and a diphenyl cyclo-sulfide group.

[0011] In some possible embodiments of the present invention, the polymeric resin includes a compound with the structural formula

[0012] as follows.

[0013] In some possible embodiments of the present invention, the refractive index of the polymeric resin is higher than 1.8; or, the value of n is a positive integer between 100 and 3000.

[0014] The preparation method of the polymeric resin proposed in the second aspect of the present invention uses a first reactant with the general structural formula and a second reactant with the general structural formula to carry out a nucleophilic substitution reaction under the action of a phase transfer catalyst to obtain a product with the general structural formula as follows.

[0015] As can be seen from the above technical solutions, in the preparation method of the polymeric resin proposed in the second aspect of the present invention, the second reactant used has a group R that can provide hydrogen bonds 1, and the nitrogen atom in the triazine group that can accept hydrogen bonds and the sulfur atom with a lone pair of electrons on its side chain. The first reactant also has a hydrogen bond-accepting sulfur atom. Then, when the two are synthesized through a nucleophilic reaction, multiple hydrogen bonds with different strengths can be formed in the molecule, enhancing the intermolecular force in the polymeric resin and achieving a dense packing effect, thereby obtaining a polymeric resin with a higher refractive index and obtaining a polymeric resin with certain toughness and processability. Under the action of a phase transfer catalyst, the nucleophilic reaction has a good effect and can effectively improve the reaction efficiency.

[0016] In some possible embodiments of the present invention, the R 1 comprises an alkyl group or a hydroxyphenyl group with a carbon atom number less than or equal to 4; or, the R 2 comprises a phenyl group, a diphenyl sulfide group, or a diphenyl cyclo-sulfide group.

[0017] In some possible embodiments of the present invention, the first reactant includes 4',4-dimercapto diphenyl sulfide, thianthrene-2,7-dithiol, or 1,4-benzenedithiol; the second reactant includes 2,4-dichloro-6-methylthio-1,3,5-triazine, 2,4-dichloro-6-butylthio-1,3,5-triazine, or 2,4-dichloro-6-hydroxyphenylthio-1,3,5-triazine.

[0018] In some possible embodiments of the present invention, the phase transfer catalyst includes polyethylene glycol dialkyl ether, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogensulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, or hexadecyltrimethylammonium bromide.

[0019] In some possible embodiments of the present invention, the first reactant is first dissolved in an alkaline aqueous solution, and then a phase transfer catalyst is added and stirred at room temperature for 0.5 h to 2 h to form a first reaction solution; the second reactant is dissolved in an organic solvent to form a second reaction solution; the first reaction solution and the second reaction solution are fully stirred and reacted for 20 h to 28 h, and then poured into a purification solvent to precipitate a precipitate, obtaining a polymeric resin with the general structural formula of.

[0020] In some embodiments of the present invention, the precipitate is redissolved and precipitated one or more times for purification to obtain a polymeric resin with higher purity.

[0021] In some possible embodiments of the present invention, the organic solvent includes chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, pyridine, N-methylcaprolactam, hexamethylphosphoric triamide; the purification solvent includes n-hexane, methanol, ether or petroleum ether; alternatively, the purification solvent includes a mixed solution of a first solvent and a second solvent in a volume ratio of (9-12):(1-2), wherein the first solvent includes n-hexane, methanol, ethanol or petroleum ether, and the second solvent includes dichloromethane, ethyl acetate or tetrahydrofuran.

[0022] The optical resin proposed in the third aspect of the present invention includes: the polymerization resin of each of the foregoing embodiments; or, the polymerization resin prepared by the preparation method of each of the foregoing embodiments.

[0023] It can be seen from the above technical solutions that the optical resin proposed in the third aspect of the present invention can obtain the advantages brought by the polymerization resin by adopting the foregoing polymerization resin, such as high refractive index, small thickness, easy processing, and certain toughness.

[0024] The optical waveguide proposed in the fourth aspect of the present invention includes the foregoing optical resin.

[0025] It can be seen from the above technical solutions that the optical waveguide proposed in the fourth aspect of the present invention has the technical effects brought by the optical resin, can be used as a resin substrate or a film layer, and is beneficial to the thinning and light-weight design of the optical waveguide.

[0026] The optical device proposed in the fifth aspect of the present invention includes the optical waveguide of the foregoing embodiment.

[0027] It can be seen from the above technical solutions that the optical device proposed in the fifth aspect of the present invention can reduce the thickness, facilitate processing, and reduce costs by adopting the foregoing optical waveguide, and the light can propagate along a predetermined optical path, the imaging is clear, and the use experience is improved.

[0028] It should be understood that the above general description and the following detailed description are only exemplary and explanatory, and cannot limit the disclosure of the embodiments of the present invention. Description of the Drawings

[0029] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly introduced below. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0030] Figure 1 It is the chemical reaction schematic diagram of the polymerization resin proposed in some embodiments of the present invention. Detailed Embodiments

[0031] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0032] Without conflict, the following embodiments and the features in the embodiments may be combined with each other.

[0033] Optical materials are mainly divided into two major categories: glass and resin, and are widely used in multiple fields such as displays, lenses, and sensors. Among them, optical resin materials are receiving increasing attention in the field of optical materials due to their advantages such as low specific gravity, high impact toughness, rich structural design, and easy processing. The refractive index of optical resin materials is one of the important indicators reflecting their material properties, and a higher refractive index can effectively improve the light efficiency. After being made into a light-transmitting material, it can also reduce the material thickness and reduce the weight.

[0034] However, the refractive indices of existing polycarbonate resin materials and resin materials cured by polythiol and isocyanate are both relatively low, not exceeding 1.7; the existing synthesis process of hydroxyl-modified polyphenylene sulfide is complex, the benzene ring is prone to oxidation and yellowing, the toughness as a resin is poor, and it is difficult to process, which limits the application of this material in the optical field.

[0035] Therefore, the present invention provides a polymeric resin, which contains various structural units such as triazine groups, aromatic groups, and substituted aromatic groups with a refractive index higher than 1.5, sulfur atoms that can increase the refractive index, groups that can provide hydrogen atoms, etc., and finally forms an amorphous stacking structure.

[0036] The polymeric resin proposed in the embodiments of the present invention has the following general structural formula as shown in Formula I:

[0037]

[0038] Among them, n is a positive integer between 1 and 10,000; R 1 is a group that can provide a hydrogen atom, and R 2 is an aromatic group or a substituted aromatic group.

[0039] Exemplarily, the value of n can be any integer between 1, 10, 20, 30, 50, 100, 200, 500, 700, 900, 1000, 2000, 3000, 5000, 7000, and 10000. Limiting the value of n within the above range can not only obtain a polymer resin with a moderate molecular weight, but also enable the entire polymer resin to form an amorphous packing structure, improving the refractive index and light transmittance of the entire polymer resin. In some further embodiments, the value of n is any value within the range of 100 to 3000 and including 100 and 3000. It is convenient for preparation, the preparation cost is more reasonable, and the structural form of the molecules formed by the entire polymer resin can remain in an amorphous packing form for a long time, bringing good processability and molecular toughness to the entire molecule.

[0040] As can be seen from the above, from the above technical solutions, it can be seen that for the polymer resin proposed in the first aspect of the present invention, its monomer contains a triazine group. The triazine group itself has a highly conjugated structure with a refractive index higher than 1.5, providing a structural basis for high refractive index for the entire polymer resin. And the monomer has S both on the main chain and the side chain, and S has a relatively high proportion in the whole molecule. S itself is a group with a high molar refractive index, and the propagation speed of light slows down when passing through, which helps to increase the refractive index of the whole molecule. The monomer also contains substituted or unsubstituted aromatic groups, and these groups also have a certain proportion, and these groups also have a relatively high conjugated structure, making a certain contribution to the formation of a high refractive index molecule.

[0041] The molecule contains rich hydrogen bond acceptors including sulfur ether, the nitrogen atom in the triazine group, and the sulfur atom with a lone pair of electrons on its side chain. The molecule also contains rich hydrogen bond donors such as the group R on the side chain of the triazine group that can provide hydrogen atoms 1 , hydrogen bonds are generated between the hydrogen bond acceptor and the hydrogen bond donor, forming multiple and unequal-strength hydrogen bond interactions in the whole molecule, enhancing the intermolecular force in the polymer resin, achieving the effect of dense packing, thereby further increasing the refractive index of the whole polymer resin, making the whole molecule of the polymer resin have a high refractive index, and the refractive index can reach above 1.8.

[0042] The main chain in the molecule of the present invention is a triazine group with a certain rigidity, an aromatic group or a substituted aromatic group with a certain rigidity, and a sulfur ether bond with a certain flexibility, enabling the molecule to have a certain rigidity while maintaining a low chain freedom degree, and making the molecular weight of the whole molecule relatively large, which is beneficial to improving the structural toughness and processability of the whole molecule, and can also make the whole polymer resin have good thermal stability, a low shrinkage rate, and good mechanical properties, so that the whole molecule has good processability.

[0043] In addition, S has a relatively large atomic radius, and it is not easy to form a conjugated structure between groups and atoms, as well as between groups, resulting in weak light absorption. Different types and intensities of hydrogen bonds throughout the molecule can also effectively prevent the formation of an ordered crystalline structure between monomers, instead forming an amorphous packing structure, effectively avoiding light scattering and giving the polymer resin good light transmittance as a whole.

[0044] It can be understood that compared with the low-refractive-index polycarbonate resin material and the resin material cured by polythiol and isocyanate in the prior art, the refractive index of the polymer resin in this embodiment is higher than 1.8 and it has excellent light transmittance. Compared with polyphenylene sulfide in the prior art, which has a complex synthesis process and poor toughness as a resin, the polymer resin of the present invention has stable mechanical properties, good structural toughness, and is easy to process.

[0045] In some possible embodiments of the present invention, R 1 includes an alkyl group or a hydroxyphenyl group with a carbon atom number less than or equal to 4. These groups all have a certain number of hydrogen atoms, so they can provide the hydrogen atoms required for hydrogen bond interaction within the polymer resin molecule. Alkyl groups with a carbon atom number less than or equal to 4, such as methyl, ethyl, propyl, or butyl, selecting different types of alkyl groups can provide alkane side chains of different lengths, providing an internal plasticization effect for the whole molecule and making the molecules of the whole polymer resin have good strength and toughness at the same time.

[0046] In some possible embodiments of the present invention, R 2 includes phenyl, diphenyl sulfide group, and diphenyl cyclo-sulfide group. Most of these groups are aromatic unsaturated groups, which can effectively increase the proportion of the conjugated structure in the molecule, thereby increasing the refractive index and stiffness of the molecule. In addition, the diphenyl sulfide group and diphenyl cyclo-sulfide group here further provide the number of S atoms in the molecule and can provide a lower chain freedom degree, which is beneficial to further improving the toughness and chain freedom degree of the whole molecule.

[0047] In some possible embodiments of the present invention, the polymer resin includes a compound with the structural formula

[0048]

[0049] as follows.

[0050] In the polymer molecules of these examples, the N in the triazine structure, the S in the triazine side chain, and the thioether in the main chain can all serve as hydrogen bond acceptors, while the O-H and C-H in the triazine side chain can serve as groups providing hydrogen bonds, which enables the entire polymer resin molecule to contain both abundant hydrogen bond donors and hydrogen bond acceptors. Then, when the hydrogen bond donors and hydrogen bond acceptors on different monomers in the polymer resin molecule combine, multiple hydrogen bonds with unequal forces are formed, making the entire molecule denser; in addition, the molecule also contains S atoms with relatively large atomic radii, which is conducive to the formation of an amorphous dense packing structure by the entire molecule, thereby achieving a refractive index of the polymer resin of the present invention higher than 1.8 and having good light transmittance.

[0051] In some possible embodiments of the present invention, the refractive index of the polymer resin is higher than 1.8. Then the polymer resin of the present invention can be applied to optical waveguides, especially when made into lenses, the lens has a small thickness, high light efficiency, low processing cost, and good wearing experience.

[0052] The preparation method of the polymer resin of the present invention is described below.

[0053] The preparation method of the polymer resin proposed by the present invention, in combination Figure 1 as shown, uses a first reactant with a structural general formula of and a second reactant with a structural general formula of to carry out a nucleophilic substitution reaction under the action of a phase transfer catalyst to obtain a product with a structural general formula of .

[0054] From the above structure, it can be seen from the above technical solution that the preparation method of the polymer resin proposed by the present invention uses a second reactant that simultaneously has a group capable of providing hydrogen bonds such as R 1 , and a group capable of accepting hydrogen bonds such as the nitrogen atom in the triazine group and the sulfur atom with lone pairs on its side chain. The first reactant also has a sulfur atom that can accept hydrogen bonds. Then, when the two are synthesized through a nucleophilic reaction, multiple hydrogen bond interactions with unequal strengths can be formed in the molecule, enhancing the intermolecular forces in the polymer resin and achieving a dense packing effect, thereby obtaining a polymer resin with a relatively high refractive index and obtaining a polymer resin with certain toughness and processability.

[0055] In the present invention, R 1As an electron-donating group, it can activate the adjacent chlorine atom in the second reactant, making it more likely to participate in the reaction; the mercapto group -SH in the first reactant, as a strong nucleophilic group, is more likely to make the first reactant attack -Cl in the second reactant as a nucleophile under the action of a phase transfer catalyst, with a good nucleophilic reaction effect. Eventually, the -Cl on the triazine group leaves and can form a thioether bond with -SH in the first reactant, thereby forming a polymer molecule with the structure required in this application. Meanwhile, by controlling the amounts of each reactant, the degree of polymerization n can also be effectively adjusted, thereby effectively controlling the structure and morphology of the finally generated polymer molecule.

[0056] In the selection of the type of R 1 group in the present invention, in addition to considering the specific function of the group, factors such as the easy availability of the second reactant, reasonable processing cost, or convenient preparation also need to be taken into account.

[0057] In some possible embodiments of the present invention, R 1 includes an alkyl group or a hydroxyphenyl group with a carbon atom number less than or equal to 4. As mentioned above, an alkyl group with a carbon atom number less than or equal to 4, such as methyl, ethyl, propyl, or butyl, selecting different types of alkyl groups can provide alkane side chains of different lengths, providing an internal plasticizing effect for the whole molecule and endowing the molecules of the whole polymeric resin with good strength and toughness. In addition, these alkyl groups are connected to the sulfur atom and together serve as a side chain of the triazine group, and also have the effect of activating the adjacent chlorine atom in the second reactant, making the nucleophilic substitution reaction with the first reactant easier to proceed. The hydroxyphenyl group can not only provide hydrogen atoms but also activate the adjacent chlorine atom in the second reactant, thereby also making Cl- more likely to leave, facilitating the synthesis of the final polymer molecule with the first reactant.

[0058] In some examples, the second reactant includes 2,4-dichloro-6-methylthio-1,3,5-triazine. Then, here, the methylthio group, as an electron-donating group, can activate the adjacent chlorine atom in the second reactant, making it more likely to participate in the reaction. The methyl group also serves as a group providing hydrogen atoms. The methyl group can form a hydrogen bond with the S it is connected to, and the methyl group can also form a hydrogen bond with the N on the triazine group. After the synthesis of the first reactant and the second reactant, the methyl group can also form a hydrogen bond with the S of the thioether group, thereby forming multiple hydrogen bonds with different interaction strengths within the polymer molecule, which is beneficial to the formation of an amorphous stacking structure.

[0059] In some examples, the second reactant includes 2,4-dichloro-6-butylthio-1,3,5-triazine. Here, the butylthio group, as an electron-donating group, can activate the adjacent chlorine atoms in the second reactant, making them more likely to participate in the reaction. The butyl group also serves as a hydrogen atom-providing group. The butyl group can form a hydrogen bond with the S it is connected to, and the butyl group can also form a hydrogen bond with the N on the triazine group. After the synthesis of the first reactant and the second reactant, the butyl group can also form a hydrogen bond with the S of the thioether group, thus forming multiple hydrogen bonds with different interaction strengths within the polymer molecule, which is beneficial to the formation of an amorphous stacking structure.

[0060] In some examples, the second reactant includes 2,4-dichloro-6-hydroxybenzene thio-1,3,5-triazine. Here, the hydroxybenzene thio group, as an electron-donating group, can activate the adjacent chlorine atoms in the second reactant, making them more likely to participate in the reaction. The hydroxyl group in the hydroxybenzene group also serves as a hydrogen atom-providing group. The hydroxyl group in the hydroxybenzene group can form a hydrogen bond with the S it is connected to, and the hydroxyl group in the hydroxybenzene group can also form a hydrogen bond with the N on the triazine group. After the synthesis of the first reactant and the second reactant, the hydroxyl group in the hydroxybenzene group can also form a hydrogen bond with the S of the thioether group, thus forming multiple hydrogen bonds with different interaction strengths within the polymer molecule, which is beneficial to the formation of an amorphous stacking structure. In these examples, the following method can be used to prepare 2,4-dichloro-6-hydroxybenzene thio-1,3,5-triazine: The first step is the synthesis of 6-hydroxy-2,4-dichloro-1,3,5-triazine: In a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, cyanuric chloride is dissolved in acetonitrile, an appropriate amount of water is slowly added, and the mixture is stirred at 0 °C to 5 °C for 18 hours. After post-treatment and purification, the product is obtained. The second step is the synthesis of 2,4-dichloro-6-hydroxybenzene thio-1,3,5-triazine: The product generated in the first step is dissolved in DMF (dimethylformamide), potassium carbonate and benzenethiol are added, and the mixture is stirred at 50 °C for 20 hours. After post-treatment and purification, the product - 2,4-dichloro-6-hydroxybenzene thio-1,3,5-triazine can be obtained.

[0061] In some possible embodiments of the present invention, R 2 includes a phenyl group, a diphenyl sulfide group, and a diphenyl cyclo sulfide group. As mentioned before, most of these groups are aromatic unsaturated groups, which can provide more conjugated structures for the finally formed polymer molecules, thereby increasing the refractive index and molecular stiffness of the finally synthesized polymer molecules. In addition, the diphenyl sulfide group and the diphenyl cyclo sulfide group in the R 2 group further provide S atoms or thioether bonds, thus providing the structural basis required for generating polymer molecules with lower chain degrees of freedom.

[0062] In some examples, the first reactant includes 4',4-dimercapto diphenyl sulfide. In these examples, there are two mercapto groups in the molecule of the first reactant, which have strong nucleophilicity and also provide a structural basis for the formation of thioether bonds in the polymeric resin; the two phenyl groups in the molecule of the first reactant provide more conjugated structures, and the thioether groups in the molecule not only provide sulfur atoms but also provide lower chain degrees of freedom. The refractive index of the diphenyl sulfide group is greater than 1.6. The beneficial effects brought by the conjugated structure, sulfur atoms and thioether groups have been described above and will not be elaborated here; using this first reactant can achieve an efficient nucleophilic reaction with the second reactant and can also form a polymeric resin with high refractive index, good light transmittance and good processability.

[0063] In some examples, the first reactant includes thianthrene-2,7-dithiol. In these examples, there are also two mercapto groups in the molecule of the first reactant, which also have strong nucleophilicity and also provide a structural basis for the formation of thioether bonds in the polymeric resin. The two phenyl groups in the molecule of the first reactant can also provide more conjugated structures for the synthesis of the polymeric resin, and the cyclic thioether groups in the molecule also provide sulfur atoms and lower chain degrees of freedom. Then, using this first reactant can achieve an efficient nucleophilic reaction with the second reactant and form a polymeric resin with high refractive index, good light transmittance and good processability.

[0064] In some examples, the first reactant includes 1,4-benzenedithiol. In these examples, there are two mercapto groups in the molecule of the first reactant, which have strong nucleophilicity and also provide a structural basis for the formation of thioether bonds in the polymeric resin. The phenyl group in the molecule of the first reactant provides more conjugated structures for the formed polymeric resin; the beneficial effects brought by the conjugated structure have been described above and will not be elaborated here. Then using this first reactant can achieve an efficient nucleophilic reaction with the second reactant and form a polymeric resin with high refractive index, good light transmittance and good processability.

[0065] In some possible embodiments of the present invention, the phase transfer catalyst includes polyethylene glycol dialkyl ether, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogensulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride or cetyltrimethylammonium bromide. These phase transfer catalysts can promote the transfer of reactants between different phases. For example, they can promote the transfer of reactants in the organic phase to the aqueous phase, or promote the transfer of reactants in the aqueous phase to the organic phase, thereby improving the reaction efficiency of the entire nucleophilic reaction and promoting the smooth progress of the reaction.

[0066] In some possible embodiments of the present invention, the first reactant is first dissolved in an alkaline aqueous solution, and then a phase transfer catalyst is added and stirred at room temperature for 0.5 h to 2 h to form a first reaction solution; the second reactant is dissolved in an organic solvent to form a second reaction solution; the first reaction solution and the second reaction solution are fully stirred and reacted for 20 h to 28 h, and then poured into a purification solvent to precipitate a precipitate, obtaining a polymeric resin with the structural general formula The phase transfer catalyst and its functions in these examples are as described above and will not be elaborated here. The first reactant in these examples is dissolved in an alkaline aqueous solution, which can provide an alkaline environment for facilitating the reaction with the second reactant. Specifically, when Cl in the second reactant leaves and HCl is generated, it can be consumed in the alkaline environment, enabling the reaction to proceed faster. The alkaline aqueous solution mentioned in these examples can be a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, or other easily available alkaline aqueous solutions.

[0067] In the above examples, stirring for 0.5 h to 2 h can be for 0.5 h, 1 h, 1.5 h, 2 h or other times, which is not limited here. When the first reactant and the phase transfer catalyst are stirred in the alkaline aqueous solution for the above duration, the first reaction solution can be fully mixed, ensuring that the entire reaction solution is relatively homogeneous, which is beneficial for the subsequent reaction to be more thorough and can also reasonably control the reaction operation time. The first reaction solution and the second reaction solution are fully stirred and reacted for 20 h to 28 h. For example, it can be 20 h, 21 h, 22 h, 23 h, 24 h, 25 h, 26 h, 27 h or 28 h, which is not limited here. When the first reaction solution and the second reaction solution are stirred and reacted for the above duration, the nucleophilic reaction can occur completely and the reaction is more thorough; it can also control the preparation operation time within a reasonable range.

[0068] In the above examples, the organic solvent can be solvents such as chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, pyridine, N-methylcaprolactam, hexamethylphosphoramide, etc., which is not limited here. The organic solvent here can achieve high compatibility with the second reactant, have good solubility with the product, and is also convenient for separating from the product later and is easy to obtain and has strong operability.

[0069] In the above examples, the purification solvent can be any one of n-hexane, methanol, ether or petroleum ether, or any ratio of several solvents. The solubility of the precipitate in the purification solvent is low. Then, when the purification solvent is added to the reaction system, the product will easily precipitate and be separated from the liquid phase.

[0070] In some embodiments, the precipitate in the foregoing examples is redissolved one or more times and then precipitated and purified to obtain a polymeric resin with higher purity.

[0071] Then, to redissolve the precipitate, solvents such as chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, pyridine, N-methylcaprolactam, and hexamethylphosphoric triamide can be used to facilitate the dissolution of the product and the removal and separation from the reactants.

[0072] In the above example, the purification solvent for purification after dissolution can be selected from one or more solvents such as methanol, ethanol, petroleum ether, etc. In addition, in addition to the first solvent such as n-hexane, methanol, ethanol, petroleum ether, etc., the purification solvent selected for re-purification can also be added with a certain proportion of a second solvent such as dichloromethane, ethyl acetate, tetrahydrofuran, etc., to improve the compatibility of the purification solvent with the solvent used for dissolution. One or more solvents are combined, and the combined solution should have a lower solubility in the product so that the product can precipitate. The combined solution can improve the compatibility with the organic solvent used for dissolution, so that the entire purification system can be mixed faster, which is conducive to rapid precipitation and purification. In the mixed solution after combination, the volume ratio of the first solvent to the second solvent is (9-12): (1-2).

[0073] For example, in some examples, a mixed solution of methanol (first solvent) and dichloromethane (second solvent) in a volume ratio of (9-12): (1-2) can be selected, for example, a volume ratio of 9:1, 10:1, 11:1.5, 12:2, etc. can be used. Alternatively, a mixed solution of n-hexane (first solvent) and dichloromethane (second solvent) in a volume ratio of (9-12): (1-2) can be selected, for example, a volume ratio of 9:1, 10:1, 11:1.5, 12:2, etc. can be used. Alternatively, a mixed solution of petroleum ether (first solvent) and ethyl acetate (second solvent) in a volume ratio of (9-12): (1-2) can be selected, for example, a volume ratio of 9:1, 10:1, 11:1.5, 12:2, etc. can be used. Alternatively, a mixed solution of ethanol (first solvent) and tetrahydrofuran (second solvent) in a volume ratio of (9-12): (1-2) is selected, for example, a volume ratio of 9:1, 10:1, 11:1.5, 12:2, etc. The solvents in these examples may also be other similar combinations, which are not limited here, as long as the purpose of precipitation and purification of the product of the present invention can be achieved, and the solvent combination selected by those skilled in the art inspired by the present invention without creative means is within the protection scope of the present invention.

[0074] In some other examples, the precipitated product is filtered and dried, and vacuum dried (for example, for 25 h to 50 h, with the required drying time being selected in the interval including the end values ​​of 25 h and 50 h), to obtain a white block solid, which is the polymer resin of the present invention.

[0075] Next, the optical resin of the present invention is described.

[0076] The optical resin according to the present invention includes: the polymerization resins of the foregoing respective embodiments.

[0077] The optical resin according to the present invention includes the polymerization resin prepared by the preparation method of the foregoing respective embodiments. Those skilled in the art can understand that the polymerization resin prepared by using the preparation method of the present application must have the same structure and properties as the polymerization resin claimed in the present application.

[0078] As can be seen from the above technical solutions, the optical resin proposed by the present invention can obtain the advantages brought by the polymerization resin by using the foregoing polymerization resin, such as high refractive index, small thickness, easy processing, and certain toughness.

[0079] The optical waveguide of the present invention will be described below.

[0080] The optical waveguide according to the present invention includes the foregoing optical resin.

[0081] As can be seen from the above technical solutions, the optical waveguide proposed by the present invention has the technical effects brought by the optical resin and can be used as a resin substrate or a film layer, which is beneficial to the thin and light design of the optical waveguide.

[0082] The optical device of the present invention will be described below. The optical device can be an augmented reality device (AR device, Augmented Reality), a virtual reality device (VR device, Virtual Reality), a mixed reality device (MR device, Mixed Reality), a head-up display device (HUD, Head Up Display), etc.

[0083] The optical device according to the present invention includes the optical waveguide of the foregoing embodiment.

[0084] As can be seen from the above technical solutions, the optical device proposed by the present invention can reduce the thickness, facilitate processing, and reduce costs by using the foregoing optical waveguide. The light can propagate along a predetermined optical path, the imaging is clear, and the use experience is improved. Especially when used in AR glasses, using the high-refractive-index polymerization resin of the present invention as a part of the optical waveguide can reduce the lens thickness, reduce costs, and obtain a good wearing experience.

[0085] The polymerization resin and the preparation method of the polymerization resin of the present invention will be further described below in conjunction with specific embodiments.

[0086] Example 1

[0087] The structural formula of the polymerization resin P1 in this embodiment is: wherein the value of n is 100.

[0088] Please refer toFigure 1 , select R 1 is methyl, and R 2 The preparation method of the polymeric resin P1 where R is diphenyl sulfide group includes the following steps:

[0089] Add the first reactant 4',4-dimercapto diphenyl sulfide (250.4 mg, 1 mmol) into a 10 mL container (such as a round-bottom flask), and then add 2.1 mL of 1 mol / L NaOH as an alkaline aqueous solution to dissolve and mix the first reactant; subsequently, add cetyltrimethylammonium bromide (30 mmol%, 220 mg) as a phase transfer catalyst and stir at room temperature for 1 h to form the first reaction solution. Continuously add the second reactant 2,4-dichloro-6-methylthio-1,3,5-triazine (0.5 mmol, 98 mg) dissolved in 2 ml of chloroform into the container. After vigorously stirring the two-phase solution in the container for 24 h, pour it into 60 mL of methanol, and filter and dry the white solid precipitate by suction. Dissolve the obtained white solid in 2 mL of chloroform, pour it into a 50 mL mixed solution of n-hexane and dichloromethane with a volume ratio of 10:1 to precipitate again, filter and dry the precipitated solid by suction, and vacuum dry for 48 h to obtain a white block solid, which is the polymeric resin P1.

[0090] Example 2

[0091] In this example, the structural formula of the polymeric resin P2 is: where the value of n is 180.

[0092] Please refer to Figure 1 , select R 1 is methyl, and R 2 The preparation method of the polymeric resin P2 where R is diphenyl ring sulfide group includes the following steps:

[0093] Add the first reactant thianthrene-2,7-dithiol (280.45 mg, 1 mmol) into a 10 mL container (such as a round-bottom flask), and then add 2.1 mL of 1 mol / L NaOH as an alkaline aqueous solution to dissolve and mix the first reactant; subsequently, add cetyltrimethylammonium bromide (30 mmol%, 220 mg) as a phase transfer catalyst and stir at room temperature for 1 h to form the first reaction solution. Continuously add the second reactant 2,4-dichloro-6-methylthio-1,3,5-triazine (0.5 mmol, 98 mg) dissolved in 2 ml of chloroform into the container. After vigorously stirring the two-phase solution in the container for 24 h, pour it into 60 mL of methanol, and filter and dry the white solid precipitate by suction. Dissolve the obtained white solid in 2 mL of dimethyl sulfoxide, pour it into a 50 mL mixed solution of methanol and ethyl acetate with a volume ratio of 10:1 to precipitate again, filter and dry the precipitated solid by suction, and vacuum dry for 48 h to obtain a white block solid, which is the polymeric resin P2.

[0094] Example 3

[0095] In this example, the structural formula of the polymeric resin P3 is as follows: Among them, the value of n is 350.

[0096] Please refer to Figure 1 , select R 1 to be butyl, R 2 to be diphenyl sulfide group, and the preparation method of the polymeric resin P3 includes the following steps:

[0097] Add the first reactant thianthrene-2,7-dithiol (280.45 mg, 1 mmol) into a 10 mL container (such as a round-bottom flask), and then add 2.1 mL of 1 mol / L NaOH as an alkaline aqueous solution to dissolve and mix the first reactant; subsequently, add cetyltrimethylammonium bromide (30 mmol%, 220 mg) as a phase transfer catalyst and stir at room temperature for 1 h to form a first reaction solution. Continue to add the second reactant 2,4-dichloro-6-butylthio-1,3,5-triazine (0.5 mmol, 119 mg) dissolved in 2 ml of chloroform into the container. After the two-phase solution is vigorously stirred in the container for 24 h, it is poured into 60 mL of methanol, and the white solid precipitate is filtered and dried. The obtained white solid is dissolved in 2 mL of chloroform and poured into a 50 mL mixed solution of methanol and dichloromethane with a volume ratio of 11:1 to precipitate again. The precipitated precipitate is filtered and dried, and vacuum dried for 48 h to obtain a white block solid, which is the polymeric resin P3.

[0098] Example 4

[0099] In this example, the structural formula of the polymeric resin P4 is as follows: Among them, the value of n is 800.

[0100] Please refer to Figure 1 , select R 1 to be hydroxyphenyl, R 2 to be diphenyl sulfide group, and the preparation method of the polymeric resin P4 includes the following steps:

[0101] Add the first reactant, 4',4-dimercaptodiphenyl sulfide (250.4 mg, 1 mmol), into a 10 mL container (such as a round-bottom flask), and then add 2.1 mL of a 1 mol / L NaOH aqueous solution as the alkaline aqueous solution to dissolve and mix the first reactant; subsequently, add cetyltrimethylammonium bromide (30 mmol%, 220 mg) as a phase transfer catalyst and stir at room temperature for 1 h to form the first reaction solution. Continuously add the second reactant, 2,4-dichloro-6-hydroxyphenylthio-1,3,5-triazine (0.5 mmol, 137 mg), dissolved in 2 mL of chloroform, into the container. After vigorously stirring the two-phase solution in the container for 24 h, pour it into 60 mL of methanol, and filter and dry the white solid precipitate by suction. Dissolve the obtained white solid in 2 mL of chloroform, pour it into a 50 mL mixed solution of methanol and tetrahydrofuran with a volume ratio of 9:1 to precipitate again, filter and dry the precipitated solid by suction, and vacuum dry it for 48 h to obtain a white block solid, which is the polymeric resin P4.

[0102] Example 5

[0103] In this example, the structural formula of the polymeric resin P5 is as follows: Among them, the value of n is 1800.

[0104] Please refer to Figure 1 , select R 1 to be a hydroxyphenyl group, and R 2 to be a diphenyl ring sulfide group. The preparation method of the polymeric resin P5 includes the following steps:

[0105] Add the first reactant, thianthrene-2,7-dithiol (280.45 mg, 1 mmol), into a 10 mL container (such as a round-bottom flask), and then add 2.1 mL of a 1 mol / L KOH aqueous solution as the alkaline aqueous solution to dissolve and mix the first reactant; subsequently, add cetyltrimethylammonium bromide (30 mmol%, 220 mg) as a phase transfer catalyst and stir at room temperature for 1 h to form the first reaction solution. Continuously add the second reactant, 2,4-dichloro-6-hydroxyphenylthio-1,3,5-triazine (0.5 mmol, 137 mg), dissolved in 2 mL of chloroform, into the container. After vigorously stirring the two-phase solution in the container for 24 h, pour it into 60 mL of methanol, and filter and dry the white solid precipitate by suction. Dissolve the obtained white solid in 2 mL of chloroform, pour it into a 50 mL mixed solution of ethanol and dichloromethane with a volume ratio of 12:2 to precipitate again, filter and dry the precipitated solid by suction, and vacuum dry it for 48 h to obtain a white block solid, which is the polymeric resin P5.

[0106] Example 6

[0107] In this example, the structural formula of the polymeric resin P6 is as follows:

[0108] Among them, the value of n is 2200.

[0109] Please refer to Figure 1 and select R 1 to be methyl, and the preparation method of the polymer resin P6 with R 2 being phenyl includes the following steps:

[0110] Add the first reactant, 1,4-benzenedithiol (142.2 mg, 1 mmol), into a 10 mL container (such as a round-bottom flask), and then add 2.1 mL of a 1 mol / L NaOH aqueous solution as a basic aqueous solution to dissolve and mix the first reactant; subsequently, add cetyltrimethylammonium bromide (30 mmol%, 220 mg) as a phase transfer catalyst and stir at room temperature for 1 h to form a first reaction solution. Continuously add the second reactant, 2,4-dichloro-6-methylthio-1,3,5-triazine (0.5 mmol, 98 mg), dissolved in 2 mL of chloroform, into the container. After vigorously stirring the two-phase solution in the container for 24 h, pour it into 60 mL of methanol, and filter and drain the white solid precipitate. Dissolve the obtained white solid in 2 mL of chloroform, pour it into a 50 mL mixed solution of petroleum ether and ethyl acetate with a volume ratio of 11:1 to precipitate again, filter and drain the precipitated precipitate, and dry it under vacuum for 30 h to obtain a white block solid, which is the polymer resin P6.

[0111] Example 7

[0112] In this example, the structural formula of the polymer resin P7 is:

[0113] Among them, the value of n is 3000.

[0114] Please refer to Figure 1 and select R 1 to be hydroxyphenyl, and the preparation method of the polymer resin P7 with R 2 being phenyl includes the following steps:

[0115] Add the first reactant, 1,4-benzenedithiol (142.2 mg, 1 mmol), to a 10 mL container (such as a round-bottom flask), and then add 2.1 mL of 1 mol / L NaOH as an alkaline aqueous solution to dissolve and mix the first reactant; subsequently, add cetyltrimethylammonium bromide (30 mmol%, 220 mg) as a phase transfer catalyst and stir at room temperature for 1 h to form the first reaction solution. Continue to add the second reactant, 2,4-dichloro-6-hydroxybenzenethio-1,3,5-triazine (0.5 mmol, 137 mg), dissolved in 2 mL of chloroform, to the container. After vigorously stirring the two-phase solution in the container for 24 h, pour it into 60 mL of methanol, and filter and drain the white solid precipitate. Dissolve the obtained white solid in 2 mL of chloroform, pour it into a 50 mL mixed solution of ethanol and dichloromethane with a volume ratio of 11:1 to precipitate again, filter and drain the precipitated solid, and dry it under vacuum for 30 h to obtain a white block solid, which is the polymeric resin P7.

[0116] Comparative Example

[0117] Existing polycarbonate resin material A1, resin material A2 formed by curing isocyanate group-thiol, and polyphenylene sulfide resin material A3 on the market.

[0118] Test Example

[0119] The polymeric resins P1 to P7 prepared in Examples 1 to 7 above and the resin materials A1, A2, and A3 of the comparative example were tested as follows.

[0120] 1. Refractive index test. Disperse the purified polymeric resins P1 to P7 and the resin materials A1 to A3 of the comparative example in a solvent, such as tetrachloroethane, and then spin-coat them on a silicon wafer by spin coating. After baking, use an ellipsometer to measure their refractive indices. The refractive indices of the polymeric resins P1 to P7 prepared in Examples 1 to 7 and the resin materials A1 to A3 in the comparative example obtained through testing are shown in Table 1.

[0121] 2. Abbe number test. The Abbe number is calculated from the refractive indices at wavelengths of 486. nm, 587.6 nm, and 656.3 nm, and the calculation formula is as follows:

[0122] Vd = (n D - 1) / (n F - n C )

[0123] Among them, the Abbe numbers of the polymeric resins P1 to P7 prepared in Examples 1 to 7 and the resin materials A1 to A3 in the comparative example obtained through testing are shown in Table 1.

[0124] 3. Water Absorption Test. Plate-shaped molded sheets with a thickness of 2 mm obtained by injection molding the polymer resins prepared in each example and the resin materials of the comparative examples were used to measure the water absorption after immersion at 23°C for 24 hours according to ISO62. The water absorption rates of the polymer resins P1 to P7 prepared in Examples 1 to 7 and the resin materials A1 to A3 in the comparative examples are shown in Table 1.

[0125] 4. Transmittance Test. The purified polymer resins and the resin materials of the comparative examples were respectively dispersed in a solvent such as tetrachloroethane, and then spin-coated on the surface of a glass substrate by the spin-coating method. After baking, a haze meter was used for testing. The transmittance rates of the polymer resins P1 to P7 prepared in Examples 1 to 7 and the resin materials A1 to A3 in the comparative examples are shown in Table 1.

[0126] 5. Glass Transition Temperature (Tg) Test. A 2910 type differential scanning calorimeter manufactured by TA Instruments Japan was used for testing at a heating rate of 10°C / min. The glass transition temperatures (Tg) of the polymer resins P1 to P7 prepared in Examples 1 to 7 and the resin materials A1 to A3 in the comparative examples are shown in Table 1.

[0127] 6. UV Aging Test: In a UV aging test chamber (light source power 650 mw, irradiation for 4 h, stop for 4 h as one cycle, a total of 24 cycles), the yellowing changes after UV aging of the polymer resins P1 to P7 prepared in Examples 1 to 7 and the resin materials A1 to A3 in the comparative examples are shown in Table 1.

[0128] 7. Tensile Property Test: The polymer resins of each example and the resin materials of the comparative examples were prepared into dumbbell-shaped sheets, ensuring that the surface of the specimen was smooth and free of defects, and the dimensions met the standard requirements. A steel ruler or vernier caliper was used to measure the gauge length, width, and thickness of the specimen, and the measured values were recorded. The specimen was installed on the fixture of a universal testing machine, ensuring that the specimen was firmly installed and coincided with the tensile axis. According to the type of plastic material and the test standard, parameters such as test temperature, humidity, and tensile speed were set. The testing machine was started, and a tensile load was applied to the specimen at the set tensile speed, and data such as the force-displacement curve or force-time curve during the test were recorded. According to the test data, performance indexes such as tensile strength, tensile modulus, and elongation at break were calculated.

[0129] The formula for calculating tensile strength is: σ = F max / S 0 where σ is the tensile strength, F max is the maximum load at the break of the specimen, and S 0is the initial cross-sectional area of the specimen; the formula for calculating the tensile modulus is: E = Δσ / Δε, where E is the tensile modulus, Δσ is the stress increment, and Δε is the strain increment; the formula for calculating the elongation at break is: δ = (L f - L 0 ) / L 0 × 100%, where δ is the elongation at break, L f is the gauge length at the time of specimen fracture, and L 0 is the initial gauge length of the specimen. The tensile strengths (MPa) of the polymeric resins P1 to P7 prepared in Examples 1 to 7 and the resin materials A1 to A3 in the comparative examples obtained through testing are shown in Table 1.

[0130] 8. Testing of flexural properties: Prepare long strip specimens with a rectangular cross-section that are precise in size, smooth on the surface, and free of defects from the polymeric resins of each example and the resin materials of the comparative examples according to the standard requirements; measure the width, thickness, and span of the specimens with a steel ruler or vernier caliper. The span is generally 16 times the thickness of the specimen, and record the measured values. Place the specimen steadily on the support rollers of the flexural test fixture, align the center of the specimen with the loading indenter, and ensure good contact between the specimen and the support rollers and the loading indenter. Set parameters such as the test speed and test temperature according to the characteristics of the plastic material and the test standard. Usually, the test speed is 2 mm / min or 5 mm / min, etc. Start the testing machine, apply a flexural load to the specimen at the set speed, and continuously record data such as the load-deformation curve or load-time curve until the specimen reaches the specified flexural degree or fails.

[0131] The calculation formula is σ f = 3FL / 2bh 2 , where σ f is the flexural strength, F is the maximum load during the test, L is the specimen span, b is the specimen width, and h is the specimen thickness. The calculation formula is E f = L 3 m / 4bh 3 , where E f is the flexural modulus, and m is the slope of the initial straight part of the load-deformation curve. The flexural strengths (MPa) of the polymeric resins P1 to P7 prepared in Examples 1 to 7 and the resin materials A1 to A3 in the comparative examples obtained through testing are shown in Table 1.

[0132] 9. Impact Performance Test: According to the standard requirements, prepare long strip specimens with a rectangular cross-section that are precisely sized, have a smooth surface, and no defects from the polymeric resins of each example and the resin materials of the comparative examples; use a notching device to machine notches with specified dimensions and shapes on the specimens, and measure the width and thickness of the specimens at the notches using a steel ruler or vernier caliper, accurately recording the measured values. Place the specimens stably on the supports of the testing machine, with the notches of the specimens located in the middle between the two supports and facing away from the pendulum, ensuring that the specimens are in close contact with the supports and accurately positioned. According to the characteristics of the material and the testing standard, select a pendulum with an appropriate energy and adjust the relevant parameters of the testing machine. Generally, the impact speed is 2.9 m / s or 3.8 m / s, etc. Release the pendulum to impact the specimen. After the pendulum impacts the specimen and continues to swing, the energy indicating device of the testing machine records the impact energy value absorbed by the specimen.

[0133] The calculation formula for the notched impact strength of a simply supported beam is α c = A / bh, where α c is the notched impact strength of the simply supported beam, A is the impact energy absorbed by the specimen, b is the width of the specimen at the notch, and h is the thickness of the specimen at the notch. The impact strengths (MPa) of the polymeric resins P1 to P7 prepared in Examples 1 to 7 and the resin materials A1 to A3 in the comparative examples obtained through testing are shown in Table 1.

[0134] Table 1 Performance Tests of Polymeric Resins P1 to P7 and Comparative Resin Materials A1 to A3 in Examples 1 to 7

[0135]

[0136] As can be seen from Table 1, the polymeric resins P1 to P7 prepared in Examples 1 to 7 of the present invention all have a high refractive index (refractive index greater than 1.8), which is much higher than that of the polycarbonate resin material A1 and the resin material A2 formed by curing isocyanate group - thiol in the comparative examples.

[0137] The Abbe number of each polymeric resin of the present invention is less than 30 and greater than 20, indicating that the polymeric resins P1 to P7 have no obvious dispersion, clear vision, and are comfortable to wear as materials for glasses.

[0138] The water absorption rate of each polymeric resin of the present invention is less than 0.13%, indicating that the polymeric resins P1 to P7 have a low water absorption rate and excellent waterproof performance.

[0139] The light transmittance of each polymeric resin of the present invention is greater than 85%, indicating that the polymeric resins P1 to P7 have good light transmittance and good light efficiency.

[0140] The Tg of each polymer resin of the present invention is greater than 115 °C. Then, compared with the resin material A2, the polymer resins P1 to P7 have a higher glass transition temperature, and thus have good heat resistance, oxidation resistance and stability; the difference in the glass transition temperature from the resin material A1 is not significant, but the resin material A1 has too large a change in yellowness; although the Tg of the polyphenylene sulfide resin material A3 is relatively high, the polyphenylene sulfide resin material A3 is brittle and has a large yellowness.

[0141] The change in yellowness of the polymer resins P1 to P7 of the present invention after aging is much smaller than that of the resin material A1 and the polyphenylene sulfide resin material A3 in the comparative example, indicating that the polymer resins of the present invention have excellent anti-yellowing performance.

[0142] The tensile strength of the polymer resins P1 to P7 of the present invention is comparable to that of the resin materials A1 - A3, and the tensile strength of the polymer resins of the present invention can reach 75 MPa or more. The flexural strength of the polymer resins P1 to P7 of the present invention is greater than 2500 MPa, which is higher than that of the resin materials A1 and A2. Although the flexural strength of the resin material A3 is also relatively large, its impact strength is very low. The impact strength of the polymer resins P1 to P7 of the present invention is greater than 60 kJ / m 2 . It can be seen therefrom that the polymer resins of the present invention have good processability and good structural toughness. In summary, the polymer resins of the present invention have a high refractive index (the refractive index is greater than 1.8), a high light transmittance (the light transmittance is greater than 85%), excellent waterproof performance, insignificant dispersion and can ensure clear vision, good heat resistance, excellent oxidation resistance, good stability, excellent anti-yellowing performance, good molecular structure toughness and processability.

[0143] The first reactant, the second reactant, the phase transfer catalyst, the organic solvent, the solvent, the degree of polymerization, the reaction time, etc. selected in Examples 1 to 7 of the present invention are only exemplary and should not be construed as limiting the protection scope of the present invention. For example, the phase transfer catalyst can be not only cetyltrimethylammonium bromide in the example, but also polyethylene glycol dialkyl ether, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, etc.

[0144] The above is only the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention can easily think of various equivalent modifications or substitutions, and these modifications or substitutions should all be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. A polymer resin, characterized in that It has the following general structural formula as shown in Formula I: Wherein, the value of n is a positive integer between 1 and 10000; R1 is a group that can provide a hydrogen atom, and R2 is an aromatic group or a substituted aromatic group.

2. The polymer resin according to claim 1, characterized in that R1 includes an alkyl group having 4 or less carbon atoms or a hydroxyphenyl group.

3. The polymer resin according to claim 1, characterized in that R2 includes phenyl, diphenyl sulfide, and diphenyl cyclic sulfide.

4. The polymer resin according to claim 1, characterized in that The polymer resin includes a structural formula of of compounds.

5. The polymer resin according to any one of claims 1 to 4, characterized in that The refractive index of the polymer resin is higher than 1.8; or, the value of n is a positive integer between 100 and 3000.

6. A method for preparing a polymer resin as claimed in any one of claims 1 to 5, characterized in that: The general structural formula is The first reactant and the general structural formula are The second reactant undergoes a nucleophilic substitution reaction under the action of a phase transfer catalyst to obtain a general structure of product of.

7. The method for preparing a polymer resin according to claim 6, characterized in that: The R1 includes an alkyl group with carbon atoms less than or equal to 4 or a hydroxyphenyl group; or, the R2 includes a phenyl group, a diphenyl sulfide group, or a diphenyl cyclic sulfide group.

8. The method for preparing a polymer resin according to claim 7, characterized in that: The first reactant includes 4',4-dimercaptodiphenyl sulfide, thianthrene-2,7-dithiol or 1,4-benzenedithiol; the second reactant includes 2,4-dichloro-6-methylthio-1,3,5-triazine, 2,4-dichloro-6-butylthio-1,3,5-triazine or 2,4-dichloro-6-hydroxyphenylthio-1,3,5-triazine.

9. The method for preparing a polymer resin according to any one of claims 6 to 8, characterized in that: The phase transfer catalyst includes polyethylene glycol dialkyl ether, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride or hexadecyltrimethylammonium bromide.

10. The method for preparing a polymer resin according to any one of claims 6 to 8, characterized in that: The first reactant is first dissolved in an alkaline aqueous solution, and then a phase transfer catalyst is added and stirred at room temperature for 0.5h to 2h to form a first reaction solution; the second reactant is dissolved in an organic solvent to form a second reaction solution; the first reaction solution and the second reaction solution are fully stirred and reacted for 20h to 28h, and then poured into a purification solvent to precipitate to obtain a precipitate, and the general structural formula is obtained. of polymer resin.

11. The method for preparing a polymer resin according to claim 10, characterized in that: The precipitate is redissolved once or multiple times and then separated and purified to obtain a polymer resin with higher purity.

12. The method for preparing a polymer resin according to claim 10, characterized in that: The organic solvent includes chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, pyridine, N-methylcaprolactam, hexamethylphosphoric triamide; The purification solvent includes n-hexane, methanol, ethanol or petroleum ether; or, the purification solvent includes a mixed solution of a first solvent and a second solvent in a volume ratio of (9-12):(1-2), wherein the first solvent includes n-hexane, methanol, ethanol or petroleum ether, and the second solvent includes dichloromethane, ethyl acetate or tetrahydrofuran.

13. An optical resin, characterized in that: include: A polymer resin as claimed in any one of claims 1 to 5; or a polymer resin prepared by the preparation method as claimed in any one of claims 6 to 12.

14. An optical waveguide, characterized in that: Comprising the optical resin as claimed in claim 13.

15. An optical device, characterized in that: Comprising the optical waveguide as claimed in claim 14.

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