CN117003765B - Norbornadiene sulfur-containing compound, preparation method thereof and norbornadiene optical material - Google Patents

Abstract

The application discloses a norbornadiene sulfur-containing compound, a preparation method thereof and a norbornadiene optical material, and belongs to the technical field of optical materials. The preparation method of the norbornadiene sulfur-containing compound comprises the following steps: dissolving phosphorus ylide and carbon disulfide in a first organic solvent, stirring for 4-6 hours at room temperature, filtering, and obtaining a precipitate to obtain a product A, wherein the phosphorus ylide is calculated according to the molar ratio: carbon disulfide=1: (0.5-2); adding the product A, the norbornadiene compound and the aldehyde compound into a first organic solvent, stirring for 7-24 hours at 25-70 ℃, evaporating to remove the solvent, and recrystallizing to obtain the norbornadiene sulfur-containing compound, wherein the product A is calculated by the molar ratio: norbornadiene compound: aldehyde compound = 1: (0.3-1): (0.8-2). The application solves the technical problem that the existing optical material is difficult to have both high refractive index and high Abbe number.

Description

Norbornadiene sulfur-containing compound and preparation method thereof, and norbornadiene optical material

Technical Field

The present application relates to the technical field of optical materials, and in particular to a norbornadiene sulfur-containing compound and a preparation method thereof, and norbornadiene optical materials.

Background Art

Optical polymer materials with high refractive index and high Abbe number have a wide range of potential applications, and can be used in optical lenses, anti-reflection coatings, advanced optical devices, sealants for light-emitting diode devices, etc. However, generally speaking, the higher the refractive index of an optical material, the stronger the dispersion, and the lower the Abbe number of the corresponding material; therefore, conventional optical materials have the problem of having both high refractive index and high Abbe number.

The above contents are only used to assist in understanding the technical solution of the present application and do not constitute an admission that the above contents are prior art.

Summary of the invention

The main purpose of the present application is to provide a norbornadiene sulfur-containing compound and a preparation method, and norbornadiene optical material, aiming to solve the technical problem that existing optical materials are difficult to have both high refractive index and high Abbe number.

To achieve the above-mentioned purpose, the present application provides a norbornadiene sulfur-containing compound, wherein the norbornadiene sulfur-containing compound has a structure as shown in formula (1):

Herein, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aralkyl group, an aromatic group and a heterocyclic compound; and n is an integer selected from 1 to 2.

Optionally, the norbornadiene sulfur-containing compound has a structure represented by any one of formulas (2), (3), (4) and (5).

The present application also provides a method for preparing a norbornadiene sulfur-containing compound, which is used to prepare the norbornadiene sulfur-containing compound as described above, and comprises the following steps:

Dissolve phosphorus ylide and carbon disulfide in a first organic solvent, stir at room temperature for 4-6 hours, filter, and take the precipitate to obtain product A, wherein the molar ratio of phosphorus ylide to carbon disulfide is 1:(0.5-2);

The product A, the bornadiene compound and the aldehyde compound are added to a first organic solvent, stirred at 25-70° C. for 7-24 hours, then evaporated to remove the solvent, and recrystallized to obtain a bornadiene sulfur-containing compound, wherein, in terms of molar ratio, the product A:bornadiene compound:aldehyde compound=1:(0.3-1):(0.8-2).

Optionally, the norbornadiene compound includes one or more of norbornadiene and bis(norbornadiene).

Optionally, the phosphorus ylide comprises one or more of a trialkyl phosphine and a triaryl phosphine.

Optionally, the aldehyde compound includes one or more of formaldehyde, acetaldehyde, n-butyraldehyde and benzaldehyde.

The present application also provides a norbornadiene optical material, which includes: a norbornadiene sulfur-containing compound, a polythiol compound, a second organic solvent and a photoinitiator. The norbornadiene sulfur-containing compound is the norbornadiene sulfur-containing compound as described above, and the ratio of the norbornadiene sulfur-containing compound to the polythiol compound is 1:(0.5-3) in terms of the functional group molar ratio of olefin:thiol.

Optionally, the refractive index of the norbornadiene optical material is greater than 1.6, and the Abbe number is greater than 46.

Optionally, the second organic solvent accounts for 10-30% of the total mass of the norbornadiene sulfur-containing compound and the polythiol compound, and the photoinitiator accounts for 0.5-2% of the total mass of the norbornadiene sulfur-containing compound and the polythiol compound.

Optionally, the polythiol compound includes: one or more of an aliphatic hydrocarbon polythiol compound, an alicyclic hydrocarbon polythiol compound and an aromatic hydrocarbon polythiol compound.

The present application discloses a norbornadiene optical material. The material has high optical transparency and low dispersion due to the unique structural characteristics of norbornadiene sulfur-containing compounds. The material is then combined with a polythiol compound, and the optical transparency of the material is further improved and the dispersion is reduced through the ester bonds contained in the polythiol compound, so that the Abbe number of the norbornadiene optical material is greater than 46. At the same time, due to the ring structure of the norbornadiene sulfur-containing compound, it has a smaller molar volume than the chain structure in conventional optical materials, thereby effectively improving the refractive index of the optical material. Furthermore, both norbornadiene and the polythiol compound have a high sulfur content, so that the prepared norbornadiene optical material also has a high sulfur content, and thus has a high refractive index, which is greater than 1.6.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is a schematic flow diagram of a method for preparing a norbornadiene sulfur-containing compound according to an embodiment of the present application;

FIG2 is a hydrogen nuclear magnetic resonance spectrum and a carbon nuclear magnetic resonance spectrum of the sulfur-containing norbornadiene compound prepared in Example 1 of the present application;

FIG3 is a hydrogen nuclear magnetic resonance spectrum and a carbon nuclear magnetic resonance spectrum of the sulfur-containing norbornadiene compound prepared in Example 2 of the present application;

FIG4 is a hydrogen nuclear magnetic resonance spectrum and a carbon nuclear magnetic resonance spectrum of the sulfur-containing norbornadiene compound prepared in Example 3 of the present application;

FIG5 is a hydrogen nuclear magnetic resonance spectrum and a carbon nuclear magnetic resonance spectrum of the sulfur-containing norbornadiene compound prepared in Example 4 of the present application.

The realization of the purpose, functional features and advantages of this application will be further explained in conjunction with embodiments and with reference to the accompanying drawings.

DETAILED DESCRIPTION

In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to the conventional conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

In addition, the meaning of "and/or" appearing in the full text includes three parallel solutions. Taking "A and/or B" as an example, it includes solution A, solution B, or a solution that satisfies both A and B. In addition, the technical solutions between the various embodiments can be combined with each other, but they must be based on the ability of ordinary technicians in this field to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by this application. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

In a first aspect, an embodiment of the present application provides a method for preparing a norbornadiene sulfur-containing compound. Referring to FIG. 1 , the method for preparing a norbornadiene sulfur-containing compound comprises:

Step S10, dissolving phosphorus ylide and carbon disulfide in a first organic solvent, stirring at room temperature for 4-6 hours and then filtering, taking the precipitate to obtain product A, wherein the molar ratio of phosphorus ylide to carbon disulfide is 1:(0.5-2);

Dissolve phosphorus ylide in a first organic solvent to obtain solution A; dissolve carbon disulfide in a first organic solvent to obtain solution B; then drop solution B into solution A, and after solution B is completely added, stir at room temperature for 4-6 hours; then filter and take the precipitate, and obtain product A after washing; wherein, in terms of molar ratio, phosphorus ylide: carbon disulfide = 1: (0.5-2).

Optionally, the phosphorus ylide comprises one or more of a trialkyl phosphine and a triaryl phosphine.

Preferably, the trialkylphosphine includes one or more of triethylphosphine, tributylphosphine, tri-secondary phosphine, tripropylphosphine and tripentylphosphine.

Preferably, the trialkyl phosphine includes: tributyl phosphine.

Preferably, the triaryl phosphine includes: triphenyl phosphine.

Optionally, the first organic solvent is an organic solvent that can dissolve the phosphorus ylide and the carbon disulfide; it should be understood that the function of the first organic solvent is to dissolve the phosphorus ylide and the carbon disulfide at the same time so that the phosphorus ylide and the carbon disulfide undergo a Wittig reaction (ylide reaction), that is, the first organic solvent does not participate in the reaction.

Preferably, the first organic solvent is one or more of petroleum ether and dichloromethane.

Preferably, in terms of molar ratio, phosphorus ylide: carbon disulfide = 1: (0.8-1.5).

Preferably, the molar ratio of phosphorus ylide to carbon disulfide is 1:1.

Step S20, adding the product A, the bornadiene compound and the aldehyde compound into a first organic solvent, stirring at 25-70° C. for 7-24 hours, evaporating the solvent, and recrystallizing to obtain a bornadiene sulfur-containing compound, wherein, in terms of molar ratio, the product A:bornadiene compound:aldehyde compound=1:(0.3-1):(0.8-2).

Add product A, norbornadiene compound and aldehyde compound into a first organic solvent, stir at 25-70° C. for 7-24 hours, then remove the solvent by evaporation, and recrystallize to obtain norbornadiene sulfur-containing compound; wherein, in terms of molar ratio, product A: norbornadiene compound: aldehyde compound = 1: (0.3-1):

(0.8-2).

Optionally, the norbornadiene sulfur-containing compound has a structure represented by formula (1):

Herein, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aralkyl group, an aromatic group and a heterocyclic compound; and n is an integer selected from 1 to 2.

Optionally, the norbornadiene sulfur-containing compound has a structure represented by any one of formulas (2), (3), (4) and (5).

Optionally, the norbornadiene compound includes one or more of norbornadiene and bis(norbornadiene).

Preferably, the norbornadiene compound comprises: norbornadiene.

Optionally, the aldehyde compound includes one or more of formaldehyde, acetaldehyde, n-butyraldehyde and benzaldehyde.

Optionally, the first organic solvent is an organic solvent that can dissolve the phosphorus ylide, the carbon disulfide, the norbornane compound and the aldehyde compound; it should be understood that the role of the first organic solvent is to dissolve the above substances at the same time so that a reaction occurs between the above substances, that is, the first organic solvent does not participate in the reaction.

Preferably, the first organic solvent is one or more of petroleum ether and dichloromethane.

Preferably, in terms of molar ratio, product A: norbornadiene compound: aldehyde compound = 1: (0.3-0.8): (0.8-1.4).

Preferably, in terms of molar ratio, product A: norbornadiene compound: aldehyde compound = 1:0.5:1.

In this embodiment, phosphorus ylide and carbon disulfide are dissolved by a first organic solvent to cause a Wittig reaction between phosphorus ylide and carbon disulfide, and then a norbornadiene compound and an aldehyde compound are added to generate a norbornadiene sulfur-containing compound with unique structural characteristics, so that the prepared optical material has higher optical transparency and lower dispersion, and because the ring structure of the norbornadiene sulfur-containing compound has a smaller molar volume than the chain structure in conventional optical materials, the refractive index of the optical material can be effectively improved.

A second aspect of the present application provides a method for preparing a norbornadiene optical material, the method comprising:

Step A10, stirring the norbornadiene sulfur-containing compound and the polythiol compound at a functional group molar ratio of olefin to thiol of 1:(0.5-3) until uniform, and then adding a second organic solvent and a photoinitiator to obtain a product B;

Optionally, the second organic solvent accounts for 10-30% of the total mass of the norbornadiene sulfur-containing compound and the polythiol compound, and the photoinitiator accounts for 0.5-2% of the total mass of the norbornadiene sulfur-containing compound and the polythiol compound.

Optionally, the polythiol compound includes: one or more of an aliphatic hydrocarbon polythiol compound, an alicyclic hydrocarbon polythiol compound and an aromatic hydrocarbon polythiol compound.

Optionally, the aliphatic hydrocarbon polythiol compound includes one or more of ethanedithiol, hexanedithiol, 2,3-dithio(2-mercapto)-1-propanethiol, pentaerythritol tetrakis-3-mercaptopropionate, and trimethylolpropane tris(3-mercaptopropionate).

Optionally, the alicyclic hydrocarbon polythiol compound includes one or more of 1,4-cyclohexanedithiol, cyclohexane-1,4-dimethylthiol, bicyclo[2.2.1]heptane-2,5-dithiol, and 1,4-dithiane-2,5-dithiol.

Optionally, the aromatic hydrocarbon polythiol compound includes one or more of 1,4-benzenedithiol, 1,4-benzenedimethanethiol, biphenyl-4,4'-dithiol, and 4,4'-thiodibenzenethiol.

Preferably, the polythiol compound comprises one or more of pentaerythritol tetrakis-3-mercaptopropionate, 2,3-dithio(2-mercapto)-1-propanethiol, 1,4-dithiane-2,5-dithiol, cyclohexane-1,4-dimethylthiol, 4,4'-thiodibenzenethiol and 1,4-benzenedithiol.

Preferably, the polythiol compound comprises: pentaerythritol tetrakis-3-mercaptopropionate.

Optionally, the norbornadiene sulfur-containing compound has a structure represented by formula (1):

Herein, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aralkyl group, an aromatic group and a heterocyclic compound; and n is an integer selected from 1 to 2.

Optionally, the norbornadiene sulfur-containing compound has a structure represented by any one of formulas (2), (3), (4) and (5).

Optionally, the second organic solvent is an organic solvent that can dissolve the norbornadiene sulfur-containing compound, the polythiol compound and the photoinitiator; it should be understood that the role of the second organic solvent is to simultaneously dissolve the norbornadiene sulfur-containing compound, the polythiol compound and the photoinitiator so that the norbornadiene sulfur-containing compound and the polythiol compound react, that is, the second organic solvent does not participate in the reaction.

Optionally, the second organic solvent includes: one or more of deuterated chloroform, tetrahydrofuran, toluene, nitrogen methyl pyrrolidone, ethyl acetate, dimethylformamide and dimethyl sulfoxide.

Optionally, the photoinitiator includes one or more of a free radical photoinitiator, a cationic photoinitiator and an anionic photoinitiator.

Optionally, the photoinitiator includes: one or more of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone and methyl benzoylformate.

Preferably, the norbornadiene sulfur-containing compound and the polythiol compound are stirred to be uniform at a functional group molar ratio of olefin:thiol of 1:2.

Step B20, vacuum degassing during stirring the product B to obtain a polymerizable composition for an optical material;

Step B30, initiating the optical material polymerizable composition under ultraviolet light for 20-60 minutes, and then curing at 70-100° C. for 10-20 hours to obtain a norbornadiene optical material.

Optionally, the refractive index of the norbornadiene optical material is greater than 1.6, and the Abbe number is greater than 46.

In this embodiment, the unique structural characteristics of the norbornadiene sulfur-containing compound are used to make the material have higher optical transparency and lower dispersion, and then combined with the polythiol compound, the ester bond contained in the polythiol compound further improves the optical transparency of the material and reduces the dispersion, so that the Abbe number of the norbornadiene optical material is greater than 46; at the same time, due to the ring structure of the norbornadiene sulfur-containing compound, it has a smaller molar volume than the chain structure in conventional optical materials, and thus can effectively improve the refractive index of the optical material; further, both norbornadiene and the polythiol compound have a higher sulfur content, so that the prepared norbornadiene optical material also has a higher sulfur content, and thus has a higher refractive index, which is greater than 1.6.

In order to enable the details and operations of the above embodiments of the present application to be clearly understood by those skilled in the art, and to significantly demonstrate the improved performance of the embodiments of the present application, the above technical solutions are illustrated by means of multiple embodiments below.

Example 1

0.1 mol of tributylphosphine and 0.1 mol of carbon disulfide were dissolved in petroleum ether, stirred at room temperature for 5 hours and then filtered to obtain the precipitate to obtain product A (dark red needle-shaped tributylphosphine dithiocarboxylate (84%)).

20 mmol of dark red needle-shaped tributylphosphine dithiocarboxylate, 10 mmol of norbornadiene and 20 mmol of acetaldehyde were added to dichloromethane, stirred at 25° C. for 24 h, and then the solvent was evaporated to remove, and the norbornadiene sulfur-containing compound 1 was obtained by recrystallization.

The norbornadiene sulfur-containing compound 1 was characterized by hydrogen and carbon nuclear magnetic resonance spectra, and the results are shown in FIG2 . Referring to FIG2 , it can be seen that the norbornadiene sulfur-containing compound 1 has a structure represented by formula (2).

Example 2

0.1 mol of tributylphosphine and 0.1 mol of carbon disulfide were dissolved in petroleum ether, stirred at room temperature for 5 hours and then filtered to obtain the precipitate to obtain product A (dark red needle-shaped tributylphosphine dithiocarboxylate (84%)).

20 mmol of dark red needle-shaped tributylphosphinodithiocarboxylate, 10 mmol of norbornadiene and 20 mmol of formaldehyde were added to dichloromethane, stirred at 50°C for 12 h, and then the solvent was evaporated and recrystallized to obtain norbornadiene sulfur-containing compound 2 (82%).

The norbornadiene sulfur-containing compound 2 was characterized by hydrogen and carbon nuclear magnetic resonance spectra, and the results are shown in FIG3 . Referring to FIG3 , it can be seen that the norbornadiene sulfur-containing compound 2 has a structure represented by formula (3).

Example 3

0.1 mol of tributylphosphine and 0.1 mol of carbon disulfide were dissolved in petroleum ether, stirred at room temperature for 5 hours and then filtered to obtain the precipitate to obtain product A (dark red needle-shaped tributylphosphine dithiocarboxylate (84%)).

20 mmol of dark red needle-shaped tributylphosphinodithiocarboxylate, 10 mmol of norbornadiene and 20 mmol of n-butyraldehyde were added to dichloromethane, stirred at 50°C for 24 hours, and then the solvent was evaporated and recrystallized to obtain norbornadiene sulfur-containing compound 3 (89%).

The norbornadiene sulfur-containing compound 3 was characterized by hydrogen and carbon nuclear magnetic resonance spectra, and the results are shown in FIG4 . Referring to FIG4 , it can be seen that the norbornadiene sulfur-containing compound 3 has a structure represented by formula (4).

Example 4

0.1 mol of triphenylphosphine and 0.1 mol of carbon disulfide were dissolved in dichloromethane, stirred at room temperature for 5 hours and then filtered to obtain the precipitate to obtain product A (dark red needle-shaped triphenylphosphine dithiocarboxylate (88%)).

20 mmol of dark red needle-shaped triphenylphosphine dithiocarboxylate, 10 mmol of norbornadiene and 20 mmol of benzaldehyde were added to dichloromethane, stirred at 70°C for 24 hours, and then the solvent was evaporated and recrystallized to obtain norbornadiene sulfur-containing compound 4 (90%).

The norbornadiene sulfur-containing compound 4 was characterized by hydrogen and carbon nuclear magnetic resonance spectra, and the results are shown in FIG5 . Referring to FIG5 , it can be seen that the norbornadiene sulfur-containing compound 4 has a structure represented by formula (5).

Example 5

The norbornadiene sulfur-containing compound 1 prepared in Example 1 and pentaerythritol tetrakis-3-mercaptopropionate are stirred at a functional group molar ratio of olefin to thiol of 1:2 until uniform, and then deuterated chloroform and 2-hydroxy-2-methyl-1-phenylacetone are added to obtain product B;

During the stirring process of the product B, vacuum degassing is performed to obtain a polymerizable composition for an optical material;

The optical material polymerizable composition was initiated under ultraviolet light for 30 minutes, and then cured at 70° C. for 12 hours to obtain a norbornadiene optical material 1.

The refractive index and Abbe number of the norbornadiene optical material 1 were tested, and the refractive index was n589=1.606; the Abbe number was V=57.8.

Example 6

The norbornadiene sulfur-containing compound 1 prepared in Example 1 and 2,3-dithio(2-mercapto)-1-propanethiol are stirred to be uniform at a functional group molar ratio of olefin to thiol of 1:1.8, and then nitrogen methyl pyrrolidone and 1-hydroxycyclohexyl phenyl ketone are added to obtain product B;

During the stirring process of the product B, vacuum degassing is performed to obtain a polymerizable composition for an optical material;

The optical material polymerizable composition was initiated under ultraviolet light for 40 minutes, and then cured at 70° C. for 12 hours to obtain a norbornadiene optical material 2.

The refractive index and Abbe number of the norbornadiene optical material 2 were tested, and the refractive index was n589=1.601; the Abbe number was V=57.4.

Example 7

The norbornadiene sulfur-containing compound 2 prepared in Example 2 and pentaerythritol tetrakis-3-mercaptopropionate are stirred until uniform at a functional group molar ratio of olefin to thiol of 1:2, and deuterated chloroform and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide are added to obtain product B;

During the stirring process of the product B, vacuum degassing is performed to obtain a polymerizable composition for an optical material;

The optical material polymerizable composition was initiated under ultraviolet light for 35 minutes, and then cured at 70° C. for 12 hours to obtain a norbornadiene optical material 3.

The refractive index and Abbe number of the norbornadiene optical material 3 were tested, and the refractive index was n589=1.624; the Abbe number was V=65.1.

Example 8

The norbornadiene sulfur-containing compound 2 prepared in Example 2 and 1,4-dithiane-2,5-dithiol are stirred to be uniform at a functional group molar ratio of olefin to thiol of 1:2.2, and then dimethyl sulfoxide and ethyl 2,4,6-trimethylbenzoylphenylphosphonate are added to obtain product B;

During the stirring process of the product B, vacuum degassing is performed to obtain a polymerizable composition for an optical material;

The optical material polymerizable composition was initiated under ultraviolet light for 30 minutes and then cured at 70° C. for 12 hours to obtain a norbornadiene optical material 4.

The refractive index and Abbe number of the norbornadiene optical material 4 were tested, and the refractive index was n589=1.617; the Abbe number was V=64.2.

Example 9

The norbornadiene sulfur-containing compound 3 prepared in Example 3 and pentaerythritol tetrakis-3-mercaptopropionate are stirred at a functional group molar ratio of olefin to thiol of 1:2 until uniform, and then deuterated chloroform and 2-hydroxy-2-methyl-1-phenylacetone are added to obtain product B;

During the stirring process of the product B, vacuum degassing is performed to obtain a polymerizable composition for an optical material;

The optical material polymerizable composition was initiated under ultraviolet light for 30 minutes, and then cured at 70° C. for 12 hours to obtain a norbornadiene optical material 5.

The refractive index and Abbe number of the norbornadiene optical material 5 were tested, and the refractive index was n589=1.638; the Abbe number was V=53.0.

Example 10

The norbornadiene sulfur-containing compound 3 prepared in Example 3 and 1,4-benzenedithiol were stirred to be uniform at a functional group molar ratio of olefin to thiol of 1:2, and then ethyl acetate and 1-hydroxycyclohexylphenyl ketone were added to obtain product B;

During the stirring process of the product B, vacuum degassing is performed to obtain a polymerizable composition for an optical material;

The optical material polymerizable composition was initiated under ultraviolet light for 30 minutes and then cured at 70° C. for 12 hours to obtain a norbornadiene optical material 6.

The refractive index and Abbe number of the norbornadiene optical material 6 were tested, and the refractive index was n589=1.631; the Abbe number was V=52.4.

Embodiment 11

The norbornadiene sulfur-containing compound 4 prepared in Example 4 and pentaerythritol tetrakis-3-mercaptopropionate were stirred at a functional group molar ratio of olefin to thiol of 1:2 until uniform, and then ethyl acetate and 1-hydroxycyclohexylphenyl ketone were added to obtain product B;

During the stirring process of the product B, vacuum degassing is performed to obtain a polymerizable composition for an optical material;

The optical material polymerizable composition was initiated under ultraviolet light for 30 minutes and then cured at 70° C. for 12 hours to obtain a norbornadiene optical material 7.

The refractive index and Abbe number of the norbornadiene optical material 7 were tested, and the refractive index was n589=1.643; the Abbe number was V=46.3.

Example 12

The norbornadiene sulfur-containing compound 4 prepared in Example 4 and cyclohexane-1,4-dimethylthiol are stirred until uniform at a functional group molar ratio of olefin to thiol of 1:1.8, and deuterated chloroform and 1-hydroxycyclohexyl phenyl ketone are added to obtain product B;

During the stirring process of the product B, vacuum degassing is performed to obtain a polymerizable composition for an optical material;

The optical material polymerizable composition was initiated under ultraviolet light for 30 minutes and then cured at 70° C. for 12 hours to obtain a norbornadiene optical material 8.

The refractive index and Abbe number of the norbornadiene optical material 8 were tested, and the refractive index was n589=1.641; the Abbe number was V=46.1.

The above are only preferred embodiments of the present application, and do not limit the scope of the present application. For those skilled in the art, the present application may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the scope of patent protection of the present application.

Claims (3)

1. A norbornadiene optical material, characterized in that the norbornadiene optical material is composed of the following components: a norbornadiene sulfur-containing compound, a polythiol compound, a second organic solvent and a photoinitiator, wherein the ratio of the norbornadiene sulfur-containing compound to the polythiol compound is 1:(0.5-3) in terms of the molar ratio of the functional groups of olefin:thiol; The polythiol compound is selected from: one or more of aliphatic hydrocarbon polythiol compounds, alicyclic hydrocarbon polythiol compounds and aromatic hydrocarbon polythiol compounds; The aliphatic hydrocarbon polythiol compound is selected from one or more of ethanedithiol, hexanedithiol, 2,3-dithio(2-mercapto)-1-propanethiol, pentaerythritol tetrakis-3-mercaptopropionate and trimethylolpropane tris(3-mercaptopropionate); The alicyclic hydrocarbon polythiol compound is selected from one or more of 1,4-cyclohexanedithiol, cyclohexane-1,4-dimethylthiol, bicyclo[2.2.1]heptane-2,5-dithiol and 1,4-dithiane-2,5-dithiol; The aromatic hydrocarbon polythiol compound is selected from one or more of 1,4-benzenedithiol, 1,4-benzenedimethanethiol, biphenyl-4,4'-dithiol and 4,4'-thiodibenzenethiol; The second organic solvent is selected from: one or more of deuterated chloroform, tetrahydrofuran, toluene, nitrogen methyl pyrrolidone, ethyl acetate, dimethylformamide and dimethyl sulfoxide; The photoinitiator is selected from: one or more of free radical photoinitiators, cationic photoinitiators and anionic photoinitiators; The norbornadiene sulfur-containing compound has a structure represented by any one of formulas (2), (3), (4) and (5): . 2 . The norbornadiene optical material according to claim 1 , wherein the refractive index of the norbornadiene optical material is greater than 1.6 and the Abbe number is greater than 46. 3. The norbornadiene optical material according to claim 1, wherein the second organic solvent accounts for 10-30% of the total mass of the norbornadiene sulfur-containing compound and the polythiol compound, and the photoinitiator accounts for 0.5-2% of the total mass of the norbornadiene sulfur-containing compound and the polythiol compound.