A polythiol composition, a polymerizable composition for optical material and a preparation method thereof

Abstract

The present invention belongs to the technical field of optical resins, and particularly relates to a polythiol composition, a polymerizable composition for optical materials and a preparation method thereof, wherein the polythiol composition comprises a thiol compound represented by formula (1) and a compound represented by formula (2), and the thiol compound represented by formula (1) accounts for 0.005%-6% of the total mass of the thiol compound represented by formula (1) and the compound represented by formula (2); the polymerizable composition for optical materials comprises the polythiol composition, a polyisocyanate compound, a catalyst, an ultraviolet absorber and a release agent; and the optical material composition is prepared by curing the polymerizable composition for optical materials, which can not only adjust the viscosity at the initial stage of the polymerization reaction, prolong the operable time, and simplify the reaction operation, but also has excellent optical properties.

Description

Technical Field

[0001] The invention belongs to the technical field of optical resins, and in particular relates to a polythiol composition, a polymerizable composition for optical materials and a preparation method thereof. Background Art

[0002] Plastic materials are lightweight, tough, and easy to dye. In recent years, they are often used in the preparation of various optical materials. For use in the field of eyeglass lenses, they require low specific gravity, high transparency, low yellowness, high heat resistance, high strength, and high refractive index and Abbe number. High refractive index can make the lens thinner, and high Abbe number can reduce the chromatic aberration of the lens.

[0003] As a polythiourea type optical resin material with the above excellent properties, it is an important development direction in recent years. This type of resin material is mainly prepared from polythiol compounds and isocyanate compounds as raw materials. Among them, the preparation process and performance indicators of optical resin lenses seriously restrict and affect its development trend and downstream applications. Prepolymerization (initial stage of polymerization reaction) is a very important process in the preparation of optical resin lenses. If this step is not properly controlled, not only will there be production abnormalities such as spraying, but also material grains and other phenomena in the finished product, which will lead to a decrease in the qualified rate of finished products and a decrease in the rate of excellent products. As an important performance indicator of resin lenses, the Abbe number affects the polarization and focusing of light. The higher the value, the lower the distortion rate of the lens and the better the light transmittance. However, the refractive index of the lens decreases with the increase of the Abbe number, and it is difficult to achieve a balance between high refractive index and high Abbe number. How to balance the refractive index and Abbe number is also a problem that needs to be solved urgently. Summary of the invention

[0004] In order to solve the above problems, the present invention provides a polythiol composition, a polymerizable composition for optical materials and a preparation method thereof. By introducing a thiol compound represented by formula (1) into the polythiol composition and adding a specific amount of components of the polythiol composition, the activity of the reaction can be affected in the prepolymerization reaction of the polythiol composition and the isocyanate compound, thereby effectively reducing the polymerization reaction rate, effectively regulating the viscosity in the initial stage of the polymerization reaction, extending the operation time of the next step, and effectively balancing the refractive index and the Abbe number.

[0005] The technical solution adopted by the present invention is as follows:

[0006] A polythiol composition comprises a thiol compound represented by the following formula (1) and a compound represented by the following formula (2), wherein the ratio of the thiol compound represented by the following formula (1) to the total amount of the thiol compound represented by the following formula (1) and the compound represented by the following formula (2) is 0.005%-6%. Preferably, it is 0.01%-4%, and more preferably, it is 0.05%-2%. When the ratio is low, it cannot play a role in regulating the viscosity of the prepolymerization system. When the ratio is high, the viscosity of the system will be too low, the reaction time will be too long, and the production efficiency will be affected. When the ratio is low or high, the Abbe number of the synthetic resin will be reduced. Formula (1) is mercaptoethylthiomethyl-1, and formula (2) is 2,3-dithio(2-mercapto)-1-propanethiol.

[0007]

[0008]

[0009] A polymerizable composition for optical materials comprises a polythiol composition, a polyisocyanate compound, a catalyst, an ultraviolet absorber and a release agent.

[0010] The mass ratio of the polythiol composition to the isocyanate is 1:2-0.5, preferably 1:1.8-0.7, and more preferably 1:1.5-0.9; the amount of the catalyst is 0.01%-2% of the mass of the polythiol composition and the isocyanate, preferably 0.05%-1.5%, and more preferably 0.08%-1%; the amount of the ultraviolet absorber is 0.01%-2% of the mass of the polythiol composition and the isocyanate, preferably 0.05%-1%, and more preferably 0.08%-1%; the amount of the release agent is 0.01%-2% of the mass of the polythiol composition and the isocyanate. , preferably 0.05%-1%, and more preferably 0.08%-1%.

[0011] Preferably, the isocyanate is selected from tetramethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, norbornane diisocyanate, meta-xylyl diisocyanate, tetramethyl meta-xylyl diisocyanate, dithiodipropyl diisocyanate, dithiodiethyl diisocyanate, 2,5-diisocyanatomethylthiophene, 2,5-diisocyanatomethyl-1,4-dithiane, 2,5-diisocyanato-1,4-dithiane, dihexyl thiodiisocyanate, dipropyl thiodiisocyanate, diethyl thiodi ...methyl-1,4-dithiane, dihexyl thiodiisocyanate, dipropyl thiodiisocyanate, diethyl thiodiisocyanate, 2,5-diisocyanatomethylthiophene, 2,5-diisocyanatomethylthiophene, 2,5-diisocyanatomethylthiophene, 2,5-diisocyanatomethylthiophene, 2,5-diisocyanatomethylthiophene, 2,5-diisocyanatomethylthiophene, 2,5-diisocyanatomethylthiophene, 2,5-diisocyanatomethylthiophene, 2,5-diisocyanatomethylthiophene, 2,5-diisocyanatomethylthiophene, 2,5-di One or more of diisocyanate, bis(isocyanatomethyl)adamantane, bis(isocyanatomethyl)tetrahydrothiophene, 2,6-bis(isocyanatomethyl)naphthalene, 1,5-naphthalene diisocyanate, diethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysine triisocyanate, toluene diisocyanate, o-tolidine diisocyanate, diphenylmethane diisocyanate, diphenyl ether diisocyanate, triphenylmethane triisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, etc. Preferably, one or more of hexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, and m-xylylene diisocyanate. More preferably, one of isophorone diisocyanate, norbornane diisocyanate, and m-xylylene diisocyanate.

[0012] Preferably, the catalyst is selected from one of dibutyltin dichloride, butyltin trichloride, octyltin trichloride, diphenylgermanium dichloride, and triphenylantimony dichloride. Preferably, it is one of dibutyltin dichloride, octyltin trichloride, and diphenylgermanium dichloride. More preferably, it is one of dibutyltin dichloride and octyltin trichloride.

[0013] Preferably, the ultraviolet absorber is selected from one of UV326, UV329, UV531, UV-9 and UV-541. Preferably, it is one of UV326, UV329 and UV-541, and more preferably, it is one of UV326 and UV329.

[0014] Preferably, the release agent is selected from one of isopropyl phosphate, dibutyl phosphate, octyl phosphate, isodecyl phosphate, lauryl alcohol polyoxyethylene ether phosphate, nonylphenol polyoxyethylene ether phosphate, and polyphosphate. Preferably, it is one of dibutyl phosphate, octyl phosphate, lauryl alcohol polyoxyethylene ether phosphate, nonylphenol polyoxyethylene ether phosphate, and polyphosphate. More preferably, it is one of dibutyl phosphate, lauryl alcohol polyoxyethylene ether phosphate, and polyphosphate.

[0015] A method for preparing an optical material: the optical material is prepared by curing the above-mentioned optical material with a polymerizable composition. During the preparation process: the viscosity at the initial stage of the polymerization reaction is ≤60mpa.s, and the viscosity can be maintained for ≥1.5h.

[0016] When the viscosity at the beginning of the polymerization reaction is ≤50mpa.s, this viscosity can be maintained for ≥2.5h; when the viscosity at the beginning of the polymerization reaction is ≤45mpa.s, this viscosity can be maintained for ≥3h. The lower the reaction activity, the lower the reaction rate, the lower the viscosity, and the longer the required reaction time; the higher the reaction activity, the greater the reaction rate, the greater the viscosity, and the shorter the reaction time. Therefore, by controlling the viscosity at the beginning of the polymerization reaction, the control operation time can be extended and the production efficiency can be guaranteed at the same time, spraying can be avoided, and the product can be effectively prevented from having material grains and other phenomena, thereby improving the product qualification rate and the excellent product rate.

[0017] Compared with a single polythiol compound, the polythiol composition of the present invention introduces a monofunctional thiol compound represented by formula (1), which reduces the concentration of active groups per unit volume and reduces the reaction probability between groups during the polymerization reaction, thereby effectively reducing the polymerization reaction rate, thereby effectively regulating the viscosity in the initial stage of the polymerization reaction, extending the operating time, and making the reaction simpler; after the polythiol composition introduces a cyclic thiol compound represented by formula (1) with good molecular regularity, small volume, high density and stable structure, the Abbe number of the compound can be effectively increased.

[0018] The technical solution of the present invention can be used to obtain an optical material that can effectively control the reaction activity and reaction rate, regulate the viscosity of the prepolymerization system, and extend the operation time of the next process, while having both a high Abbe number and a high refractive index, and also having excellent performance. The optical material obtained by the technical solution of the present invention effectively improves its Abbe number while ensuring a high refractive index, and has excellent properties such as a high glass transition temperature and high impact strength, which meets customer needs and has great social and economic value.

[0019] The present invention can affect the activity of the reaction in the polymerization reaction of the polythiol composition and the isocyanate compound by adding a specific amount of the polythiol composition component. The optical material prepared by the present invention can not only regulate the viscosity of the initial stage (prepolymerization) of the polymerization reaction, extend the operable time, and make the reaction easier to operate, but also has excellent optical properties, high refractive index, high Abbe number, high glass transition temperature and excellent mechanical properties. The optical material of the present invention can be used to prepare various high-precision optical material fields, such as optical glasses, optical lenses, optical filters, LED packaging materials, high reflective coatings, optoelectronic devices and many other fields, meet customer needs, and have great social and economic value. DETAILED DESCRIPTION

[0020] The invention will be further described below in conjunction with specific embodiments, so that those skilled in the art can further understand the invention, but it is not intended to limit the content of the invention. All technologies based on the principles described in the invention belong to the scope of the invention.

[0021] Viscosity: The viscosity was measured using a digital viscometer (NDJ-5S).

[0022] Refractive index: measured at 20°C using a multi-wavelength Abbe refractometer (DR-M4);

[0023] Abbe number: detected by multi-wavelength Abbe refractometer (DR-M4);

[0024] Glass transition temperature: detected by DSC-3 differential scanning calorimeter with a heating rate of 10°C / min.

[0025] The polythiol compound represented by formula (1) is mercaptoethylthiomethyl-1,4-dithiane, and the compound represented by formula (2) is 2,3-dithio(2-mercapto)-1-propanethiol.

[0026] Example 1

[0027] A method for preparing an optical material, the specific steps are as follows:

[0028] (1) Pour 1 g of dibutyltin dichloride, 0.08 g of UV326, 0.09 g of dibutyl phosphate and 52 g of hexamethylene diisocyanate into a reaction bottle according to the ratio and stir at 15 ° C for 1 h to mix well;

[0029] (2) adding 48 g of a polythiol composition (the polythiol composition comprises a thiol compound represented by formula (1) and a compound represented by formula (2), and the thiol compound represented by formula (1) accounts for 0.05% of the total mass of the polythiol composition) into a reaction flask and mixing well;

[0030] (3) After the mixture in step (2) is mixed evenly, vacuum degassing is performed for 20 minutes to obtain a mixture. The viscosity of the mixture is tested and the mixture is injected into a glass mold within a certain period of time. The glass mold is then placed in an oven and cured at 80° C. for 28 hours. The cured lens is demolded to obtain an optical material product.

[0031] Example 2

[0032] A method for preparing an optical material:

[0033] (1) Pour 0.08 g of dibutyltin dichloride, 0.1 g of UV329, 0.1 g of lauryl alcohol polyoxyethylene ether phosphate and 52 g of isophorone diisocyanate into a reaction bottle according to the ratio and stir at 20° C. for 1.5 h to mix well;

[0034] (2) adding 48 g of a polythiol composition (the polythiol composition comprises a thiol compound represented by formula (1) and a compound represented by formula (2), and the thiol compound represented by formula (1) accounts for 1% of the total mass of the polythiol composition) into a reaction flask and mixing the mixture evenly;

[0035] (3) After mixing the mixture in step (2) evenly, vacuum degas the mixture for 20 minutes to obtain a mixture. The viscosity of the mixture is tested and the mixture is injected into a glass mold within a certain period of time. The glass mold is then placed in an oven and cured at 100° C. for 24 hours. The cured lens is demolded to obtain an optical material product.

[0036] Example 3

[0037] A method for preparing an optical material:

[0038] (1) Pour 0.09 g of dibutyltin dichloride, 0.09 g of UV326, 0.08 g of octyl phosphate and 52 g of norbornane diisocyanate into a reaction bottle according to the ratio and stir at 18 ° C for 1 h to mix well;

[0039] (2) adding 48 g of a polythiol composition (the polythiol composition comprises a thiol compound represented by formula (1) and a compound represented by formula (2), and the thiol compound represented by formula (1) accounts for 2% of the total mass of the polythiol composition) into a reaction flask and mixing well;

[0040] (3) After the mixture in step (2) is evenly mixed, vacuum degassing is performed for 20 minutes to obtain a mixture, the viscosity of the mixture is tested and the mixture is injected into a glass mold within a certain period of time, and the glass mold is then placed in an oven and cured at 120° C. for 20 hours. The cured lens can be demolded to obtain an optical material product.

[0041] Example 4

[0042] A method for preparing an optical material:

[0043] (1) Pour 0.05 g of octyltin trichloride, 1 g of UV-541, 2 g of polyphosphate and 52 g of m-xylylene diisocyanate into a reaction bottle according to the ratio and stir at 15 ° C for 1.5 h to mix evenly;

[0044] (2) adding 48 g of a polythiol composition (the polythiol composition comprises a thiol compound represented by formula (1) and a compound represented by formula (2), and the thiol compound represented by formula (1) accounts for 0.01% of the total mass of the polythiol composition) into a reaction flask and mixing the mixture evenly;

[0045] (3) The mixture is obtained by vacuum degassing for 20 minutes, the viscosity of the mixture is tested and it is injected into a glass mold within a certain period of time, and then the glass mold is placed in an oven at 90° C. for curing for 26 hours. After the cured lens is demolded, the optical material product can be obtained.

[0046] Example 5

[0047] A method for preparing an optical material:

[0048] (1) Pour 1.5 g of diphenylgermanium dichloride, 0.05 g of UV329, 0.01 g of dibutyl phosphate and 52 g of hexamethylene diisocyanate into a reaction bottle according to the ratio and stir at 16° C. for 1 h to mix well;

[0049] (2) adding 48 g of a polythiol composition (the polythiol composition comprises a thiol compound represented by formula (1) and a compound represented by formula (2), and the thiol compound represented by formula (1) accounts for 4% of the total mass of the polythiol composition) into a reaction flask and mixing the mixture evenly;

[0050] (3) The mixture is obtained by vacuum degassing for 20 minutes, the viscosity of the mixture is tested and it is injected into a glass mold within a certain period of time, and then the glass mold is placed in an oven at 110° C. for curing for 22 hours. After the cured lens is demolded, the optical material product can be obtained.

[0051] Example 6

[0052] A method for preparing an optical material:

[0053] (1) Pour 2 g of dibutyltin dichloride, 0.01 g of UV326, 1 g of lauryl alcohol polyoxyethylene ether phosphate and 52 g of isophorone diisocyanate into a reaction bottle according to the ratio and stir at 18° C. for 1.5 h to mix well;

[0054] (2) adding 48 g of a polythiol composition (the polythiol composition comprises a thiol compound represented by formula (1) and a compound represented by formula (2), and the thiol compound represented by formula (1) accounts for 0.005% of the total mass of the polythiol composition) into a reaction flask and mixing well;

[0055] (3) The mixture is obtained by vacuum degassing for 20 minutes, the viscosity of the mixture is tested and it is injected into a glass mold within a certain period of time, and then the glass mold is placed in an oven and cured at 120° C. for 18 hours. After the cured lens is demolded, the optical material product can be obtained.

[0056] Example 7

[0057] A method for preparing an optical material:

[0058] (1) Pour 0.01 g of octyltin trichloride, 2 g of UV329, 0.05 g of octyl phosphate and 52 g of norbornane diisocyanate into a reaction bottle according to the ratio and stir at 20 ° C for 1 h to mix evenly;

[0059] (2) adding 48 g of a polythiol composition (the polythiol composition comprises a thiol compound represented by formula (1) and a compound represented by formula (2), and the thiol compound represented by formula (1) accounts for 6% of the total mass of the polythiol composition) into a reaction flask and mixing well;

[0060] (3) The mixture is obtained by vacuum degassing for 20 minutes, the viscosity of the mixture is tested and it is injected into a glass mold within a certain period of time, and then the glass mold is placed in an oven at 100° C. for curing for 25 hours. After the cured lens is demolded, the optical material product can be obtained.

[0061] Comparative Example 1

[0062] A method for preparing an optical material:

[0063] (1) Pour 1 g of dibutyltin dichloride, 0.08 g of UV326, 0.09 g of dibutyl phosphate and 52 g of hexamethylene diisocyanate into a reaction bottle according to the ratio and stir at 15 ° C for 1 h to mix well;

[0064] (2) Add 48 g of the compound represented by formula (2) into the reaction bottle and mix well;

[0065] (3) The mixture is obtained by vacuum degassing for 20 minutes, the viscosity of the mixture is tested and it is injected into a glass mold within a certain period of time, and then the glass mold is placed in an oven and cured at 80° C. for 28 hours. After the cured lens is demolded, the optical material product can be obtained.

[0066] Comparative Example 2

[0067] A method for preparing an optical material:

[0068] (1) Pour 0.08 g of dibutyltin dichloride, 0.1 g of UV326, 0.1 g of dibutyl phosphate and 52 g of hexamethylene diisocyanate into a reaction bottle according to the ratio and stir at 15 ° C for 1 h to mix well;

[0069] (2) adding 48 g of a polythiol composition (the polythiol composition comprises a thiol compound represented by formula (1) and a compound represented by formula (2), and the thiol compound represented by formula (1) accounts for 10% of the total mass of the polythiol composition) into a reaction flask and mixing the mixture evenly;

[0070] (3) The mixture is obtained by vacuum degassing for 20 minutes, the viscosity of the mixture is tested and it is injected into a glass mold within a certain period of time, and then the glass mold is placed in an oven and cured at 120° C. for 20 hours. After the cured lens is demolded, the optical material product can be obtained.

[0071] Comparative Example 3

[0072] A method for preparing an optical material:

[0073] (1) Pour 1 g of dibutyltin dichloride, 0.08 g of UV326, 0.09 g of dibutyl phosphate and 52 g of hexamethylene diisocyanate into a reaction bottle according to the ratio and stir at 15 ° C for 1 h to mix well;

[0074] (2) Add 48 g of a mixture into a reaction flask, wherein the mixture includes a compound represented by formula (3) and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiooctane, wherein the compound represented by formula (3) accounts for 1.5% of the total mass of the mixture, and mix them evenly; the structure of the compound represented by formula (3) is as follows:

[0075] R1 represents CH2SCH2CH2SH, R2 represents hydrogen;

[0076] (3) The mixture is obtained by vacuum degassing for 20 minutes, the viscosity of the mixture is tested and it is injected into a glass mold within a certain period of time, and then the glass mold is placed in an oven and cured at 80° C. for 28 hours. After the cured lens is demolded, the optical material product can be obtained.

[0077] The performance test results of the optical resin lenses prepared in Examples 1-7 and Comparative Examples 1-3 are shown in the following table:

[0078]

[0079] As shown in the table, the Abbe number of the optical material prepared in Examples 1-7 is ≥32.9, which is significantly greater than the Abbe number of the optical material prepared in Comparative Examples 1-3. The glass transition temperature of the optical material prepared in Examples 1-7 is ≥86.1, which is significantly greater than the glass transition temperature of the optical material prepared in Comparative Examples 1-3. It can be found that adding too much or too little of the thiol compound represented by formula (1) will affect the increase of the Abbe number and the glass softening temperature. In Comparative Example 1, the amount of the thiol compound represented by formula (1) added is 0, the viscosity at the initial stage of the polymerization reaction is relatively large, the operation time is relatively short, and production abnormalities such as spraying are prone to occur, and the finished product will cause material grains and the like. In Comparative Example 2, the amount of the thiol compound represented by formula (1) added is too large, the viscosity at the initial stage of the polymerization reaction is relatively small, and the production efficiency is affected. In Examples 1-7, a suitable proportion of the thiol compound represented by formula (1) is added, which affects the reaction rate and the viscosity at the initial stage of the polymerization reaction, so that the operation time can be appropriately extended, and the efficiency is guaranteed, thereby avoiding the problems of spraying and cracks.

[0080] The present invention can affect the activity of the reaction in the polymerization reaction of the polythiol composition and the isocyanate compound by adding a specific amount of the polythiol composition component. The optical material prepared by the present invention can not only regulate the viscosity of the initial stage (prepolymerization) of the polymerization reaction, extend the operable time, and make the reaction easier to operate, but also has excellent optical properties, high refractive index, high Abbe number, high glass transition temperature and excellent mechanical properties. The optical material of the present invention can be used to prepare various high-precision optical material fields, such as optical glasses, optical lenses, optical filters, LED packaging materials, high reflective coatings, optoelectronic devices and many other fields, meet customer needs, and have great social and economic value.

Claims

1. A polythiol composition, characterized in that The invention is composed of a thiol compound represented by the following formula (1) and a compound represented by the following formula (2); wherein the thiol compound represented by the following formula (1) accounts for 0.005% to 6% of the total mass of the thiol compound represented by the following formula (1) and the compound represented by the following formula (2); ， 。 2. A polythiol composition according to claim 1, characterized in that: The thiol compound represented by formula (1) accounts for 0.01% to 4% of the total mass of the thiol compound represented by formula (1) and the compound represented by formula (2).

3. A polythiol composition according to claim 2, characterized in that: The thiol compound represented by formula (1) accounts for 0.05% to 2% of the total mass of the thiol compound represented by formula (1) and the compound represented by formula (2).

4. A polymerizable composition for an optical material, characterized in that: The invention comprises the polythiol composition according to claim 1, a polyisocyanate compound, a catalyst, an ultraviolet absorber and a release agent.

5. The polymerizable composition for optical material according to claim 4, characterized in that: The mass ratio of the polythiol composition to the isocyanate compound is 1:2-0.5; the amount of the catalyst is 0.01%-2% of the total mass of the polythiol composition and the isocyanate; the amount of the ultraviolet absorber is 0.01%-2% of the total mass of the polythiol composition and the isocyanate; and the amount of the release agent is 0.01%-2% of the total mass of the polythiol composition and the isocyanate.

6. The polymerizable composition for optical material according to claim 5, characterized in that: The mass ratio of the polythiol composition to the isocyanate compound is 1:1.8-0.7; the amount of the catalyst is 0.05%-1.5% of the total mass of the polythiol composition and the isocyanate; the amount of the ultraviolet absorber is 0.05%-1% of the total mass of the polythiol composition and the isocyanate; and the amount of the release agent is 0.05%-1% of the total mass of the polythiol composition and the isocyanate.

7. A method for preparing an optical material, characterized in that: The optical material described in claim 4 is prepared by curing the polymerizable composition for the optical material, and during the preparation process: the viscosity at the initial stage of the polymerization reaction is ≤60mPa.s.

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