CN107200846B - Sulfur-containing optical resin material with high transmittance and high refractive index and preparation method thereof - Google Patents
Sulfur-containing optical resin material with high transmittance and high refractive index and preparation method thereof Download PDFInfo
- Publication number
- CN107200846B CN107200846B CN201611151468.6A CN201611151468A CN107200846B CN 107200846 B CN107200846 B CN 107200846B CN 201611151468 A CN201611151468 A CN 201611151468A CN 107200846 B CN107200846 B CN 107200846B
- Authority
- CN
- China
- Prior art keywords
- solution
- ethanol
- stirring
- butyl acetate
- mass ratio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/06—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols from sulfides, hydropolysulfides or polysulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
A sulfur-containing optical resin material with high transmittance and high refractive index and a preparation method thereof are disclosed, the preparation method comprises the following steps: reacting 1,3, 5-tribromomethylbenzene with thiourea, preparing isothiourea salt by using ethanol-n-butyl acetate as a solvent, and then adding sodium hydroxide for hydrolysis; extracting with chloroform, and adsorbing impurities with attapulgite to obtain high-purity colorless 1,3, 5-trimercaptomethylbenzene; 1,3, 5-trithiol methyl benzene and isocyanate are subjected to polymerization reaction to prepare the optical resin material with high refractive index and high light transmittance. The 1,3, 5-trimercaptomethylbenzene compound prepared by the method has high purity, and the monomer and resin materials have the advantages of high refractive index, high transmittance and the like, wherein the light transmittance of the 1,3, 5-trimercaptomethylbenzene is more than or equal to 89%, the refractive index is more than or equal to 1.65, and the yellow index is less than or equal to 1; the light transmittance of the resin material is more than or equal to 90 percent, the refractive index is more than or equal to 1.66, and the yellow index is less than or equal to 1.50.
Description
Technical Field
The invention relates to a preparation method of a high-transmittance and high-refraction sulfur-containing optical resin material, in particular to a method for preparing a high-purity 1,3, 5-trithiol methyl benzene monomer, and carrying out a curing reaction with an isocyanate compound to prepare an optical resin material and a lens with high transmittance and high refractive index.
Background
The optical resin polymer contains sulfur, so that the refractive index can be greatly improved, the dispersion can be reduced, and the Abbe number can be increased. The polythiol compound is a monomer for preparing sulfur-containing optical resin, and has the advantages of high refraction, low dispersion, good heat resistance and weather resistance, and the like. There are various synthetic methods for polythiol compounds, and common synthetic methods include hydrocarbylation of thiourea, addition of olefin to hydrogen sulfide, hydrocarbylation of sodium (potassium) hydrosulfide, hydrolysis of thiol ester, disulfide reduction, reaction of metal organic compound with sulfur, reduction of sulfonyl chloride, and the like, for example, the following synthetic methods:
1. reaction of olefins with hydrogen sulfide
2. Reaction of thiourea with bromoalkane
3. Preparation of disulfides and alkali metal halides
4. Reaction of alcohols with hydrogen sulfide
The indexes of the refractive index, the light transmittance and the yellow index of the ternary mercaptan compound are greatly influenced by the processing temperature and the synthesis process. When mercaptan is prepared by a traditional thiourea alkylation hydrolysis method, as some substances generate mono-substituted mercaptan, di-substituted mercaptan and azo structure byproducts in the reaction process, the product is yellow, the refractive index, the transmittance and the purity of a mercaptan monomer are influenced, and the product is used as an optical material and is not suitable for manufacturing high-precision lenses and optical devices.
Disclosure of Invention
The invention prepares the optical resin material and the lens with high transmittance and high refractive index by preparing the high-purity 1,3, 5-trithiol methyl benzene monomer and carrying out curing reaction with isocyanate compounds. The product prepared by the method has high refractive index, high light transmittance and low yellow index.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for preparing a sulfur-containing optical resin material with high transmittance and high refractive index comprises the following steps:
I. preparation of isothiourea salts: adding a mixed solvent of 1,3, 5-tribromomethylbenzene and ethanol-n-butyl acetate into a reaction vessel, and stirring and uniformly dispersing at room temperature; wherein the ethanol and the n-butyl acetate are mixed according to the mass ratio of (5.5-6.5) to 1, and the mass ratio of the 1,3, 5-tribromomethylbenzene to the mixed solvent is 1 to (20-30); then adding thiourea, stirring for 20-24 hours, wherein the mass ratio of the thiourea to the 1,3, 5-tribromomethylbenzene is (0.5-1.2) to 1, and a large amount of white precipitates are separated out from the solution; filtering, washing the precipitate with ethanol-n-butyl acetate mixed solution, filtering for 2-3 times, mixing ethanol and n-butyl acetate in the ethanol-n-butyl acetate mixed solution at a mass ratio of (4.5-5.5) to 1, and drying to obtain white isothiourea salt;
II, adding alkali for hydrolysis: adding isothiourea salt into distilled water with the weight of 20-30 times, stirring and dissolving until the solution is clear, adding sodium hydroxide flake caustic soda, heating and refluxing for 4-5 hours, and cooling to room temperature, wherein the mass ratio of the sodium hydroxide to the 1,3, 5-tribromomethylbenzene used in the step I is (0.5-1) to 1;
acidification to generate thiols: cooling the system to 10-20 ℃ by using an ice bath, dropwise adding hydrochloric acid to adjust the pH value of the system to 3-3.5, extracting by using trichloromethane to obtain an organic phase solution containing the ternary mercaptan, and washing the organic phase solution to be neutral by using distilled water;
and IV, decoloring and purifying: drying the solution obtained in the step III to remove water, adding an attapulgite adsorbent, wherein the addition amount of the adsorbent is equal to the mass of thiourea used in the step I, stirring and mixing for 35-45 minutes, standing for 2-3 hours, adsorbing a small amount of azo chromophore in the solution, removing the attapulgite adsorbent, and evaporating to remove the solvent to obtain high-purity colorless 1,3, 5-trithiol methyl benzene;
v, curing reaction: and (3) taking dibutyltin dilaurate as a catalyst, and carrying out curing reaction on the 1,3, 5-trithiol methylbenzene obtained in the step IV and isocyanate to prepare the sulfur-containing optical resin material with high transmittance and high refractive index.
The preparation method is characterized in that the particle size of the attapulgite adsorbent is 100-400 meshes.
The preparation method as described above, characterized in that the specific operations of step V are: mixing 1,3, 5-trimercapto methyl benzene and isocyanate compounds according to the molar ratio of (0.7-1.3) to (1-2); adding a catalyst dibutyltin dilaurate accounting for 1-3 wt% of 1,3, 5-trimercaptomethyl benzene, adding an auxiliary agent, then carrying out prepolymerization on the mixture at 58-62 ℃ for 35-45min, pouring the raw material into a mold after vacuum deaeration, heating the raw material to 90-130 ℃ for curing and molding, then slowly cooling to room temperature, demolding and cleaning to obtain the colorless transparent optical resin material.
The preparation method is characterized in that the molar ratio of the 1,3, 5-trimercaptomethylbenzene to the isocyanate compound is (0.7-1) to (1-1.5).
The production method as described above, wherein the isocyanate compound is one or a mixture of at least one of toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, 1, 6-hexamethylene diisocyanate, m-xylylene diisocyanate, naphthalene-1, 5-diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, and isophorone diisocyanate.
The preparation process as described above, characterized in that it comprises the following operative steps:
I. preparation of isothiourea salts: adding a mixed solvent of 1,3, 5-tribromomethylbenzene and ethanol-n-butyl acetate into a reaction vessel, and stirring and uniformly dispersing at room temperature; wherein ethanol and n-butyl acetate are mixed according to the mass ratio of 6: 1, and the mass ratio of the 1,3, 5-tribromomethylbenzene to the mixed solvent is 1: 25; then adding thiourea, stirring for 24 hours, wherein the mass ratio of the thiourea to the 1,3, 5-tribromomethylbenzene is 3: 4, and a large amount of white precipitates are separated out from the solution; filtering, washing the precipitate with ethanol-n-butyl acetate mixed solution, filtering for 3 times, mixing ethanol and n-butyl acetate in the ethanol-n-butyl acetate mixed solution at a mass ratio of 5: 1, and drying to obtain white isothiourea salt;
II, adding alkali for hydrolysis: adding isothiourea salt into distilled water with the weight of 25 times, stirring and dissolving until the solution is clear, adding sodium hydroxide flake alkali, wherein the mass ratio of sodium hydroxide to the 1,3, 5-tribromomethylbenzene used in the step I is 3: 4, heating and refluxing for 5 hours, and cooling to room temperature;
acidification to generate thiols: cooling the system to below 20 ℃ by using an ice bath, dropwise adding hydrochloric acid to adjust the pH value of the system to 3, extracting by using trichloromethane to obtain an organic phase solution containing the ternary mercaptan, and washing the organic phase solution to be neutral by using distilled water;
and IV, decoloring and purifying: drying the solution obtained in the step III to remove water, adding an attapulgite adsorbent, wherein the addition amount of the adsorbent is equal to the mass of thiourea used in the step I, stirring and mixing for 40 minutes, standing for 2.5 hours, adsorbing a small amount of azo chromophore in the solution, removing the attapulgite adsorbent, and evaporating to remove the solvent to obtain high-purity colorless 1,3, 5-trimercapto methylbenzene;
v, curing reaction: mixing 1,3, 5-trimercapto methyl benzene and isocyanate compounds according to the molar ratio of (0.7-1) to (1-1.5); adding a catalyst dibutyltin dilaurate accounting for 1-3 wt% of 1,3, 5-trimercaptomethyl benzene, adding an auxiliary agent, then carrying out prepolymerization on the mixture at 60 ℃ for 40min, pouring the raw material into a mold after vacuum defoaming, heating the raw material to 90-130 ℃ to solidify and mold the raw material, then slowly cooling to room temperature, demolding and cleaning to obtain the colorless transparent optical resin material.
In another aspect, the present invention provides a high transmittance, high refractive index sulfur-containing optical resin material, which is prepared by the method as described above.
In yet another aspect, the present invention provides a high transmittance, high refractive index sulfur-containing optical resin lens prepared by the method as described above.
The synthetic route of the 1,3, 5-trimercaptomethylbenzene monomer is as follows:
in the synthesis method of the 1,3, 5-trimercaptomethylbenzene, the step of preparing the isothiourea salt adopts an ethanol-n-butyl acetate mixed solvent. The tri-substituted isothiourea salt is not easy to dissolve in an ethanol-n-butyl acetate mixed solvent, but the mono-substituted thiourea salt, the di-substituted thiourea salt and the bromomethyl can be completely dissolved, so that the by-products of the mono-substituted thiourea salt and the di-substituted thiourea salt can be effectively separated, and the product with extremely high purity is obtained. In the experimental process, it can be observed that after the tribromomethylbenzene and the thiourea react, the system is clear, and after the reaction is continued for a period of time to generate the tri-substituted isothiourea salt, a large amount of pure white solid can be separated out. In addition, few azo chromophores are generated in the heating process, so that the product is yellowed, the purity and the transparency of the product are influenced, and the attapulgite adsorbent is selected to remove byproducts through repeated tests, so that the effect is obvious.
The method has the beneficial effects that the 1,3, 5-trithiol methyl benzene prepared by the method has high purity and low yellow index, and the isocyanate resin lens prepared by the method has high light transmittance, high refractive index and low yellow index. Wherein the light transmittance of the 1,3, 5-trithiol methyl benzene is more than or equal to 89%, the refractive index is more than or equal to 1.65, and the yellow index is less than or equal to 1; the light transmittance of the resin lens is more than or equal to 90 percent, the refractive index is more than or equal to 1.66, and the yellow index is less than or equal to 1.50.
Drawings
FIG. 1 is a FT-IR infrared spectrum of 1,3, 5-trimercaptomethylbenzene prepared in example 1.
FIG. 2 is a HNMR NMR spectrum of 1,3, 5-trimercaptomethylbenzene prepared in example 1.
FIG. 3 is a CNMR NMR carbon spectrum of 1,3, 5-trimercaptomethylbenzene prepared in example 1.
FIG. 4 is a graph showing a comparison of the transmittance spectra of 1,3, 5-trimercaptomethylbenzene.
FIG. 5 is a graph showing a comparison of transmittance spectra of resin lenses.
Detailed Description
The invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention.
Example 1: preparation of 1,3, 5-trimercaptomethyl benzene trithiol monomer and optical resin lens
(1) Preparation of 1,3, 5-trimercaptomethylbenzene: adding 40g of 1,3, 5-tribromomethylbenzene into a four-mouth bottle, adding 1000mL of mixed solution of ethanol and n-butyl acetate, wherein the ethanol and the n-butyl acetate are prepared according to the mass ratio of 6: 1, stirring and dispersing uniformly by using magnetons, then adding 30g of thiourea, stirring for 24 hours, separating out a large amount of white precipitate, mixing the white precipitate with ethanol and the n-butyl acetate according to the mass ratio of 5: 1 by filtering, washing and filtering for 3 times, and drying to obtain white isothiourea salt; continuously adding 1000mL of distilled water, stirring and dissolving until the solution is clear, then adding 30g of NaOH, heating and refluxing for 5 hours, and cooling to room temperature; cooling the system by using an ice bath, dropwise adding hydrochloric acid, adjusting the pH value of the system to 3, extracting by using 300mL multiplied by 3 of trichloromethane to obtain an organic phase solution containing the ternary mercaptan, and washing the organic phase solution to be neutral by using distilled water; and (3) stirring and adding 30g of attapulgite adsorbent after dehydration, stirring and mixing for 40 minutes, standing for 2.5 hours, adsorbing a small amount of azo chromophore in the solution, removing the lower attapulgite adsorbent layer by layer, and evaporating to remove the solvent to obtain 15.6g of high-purity colorless 1,3, 5-trimercapto methyl benzene.
Infrared spectrum detection and analysis: infrared spectrum (FIG. 1) of 2554.26cm after coating 1,3, 5-trimercaptomethylbenzene on potassium bromide salt tablets-1The absorption peak is the stretching vibration peak of the S-H bond of the liquid aliphatic mercaptan, which is the characteristic peak for identifying the S-H group, and the generation of the sulfydryl in the reaction step is verified; 708.37cm-1The absorption peak is the stretching vibration of the C-S bond; 1600.67cm-1And 1453.50cm-1The two absorption peaks appear in a double-peak mode, and are skeleton vibration of a benzene ring, including carbon stretching vibration of inner carbon in the ring and the like; 3000cm-1The nearby absorption peak is the C-H stretching vibration on the benzene ring.
Detecting and analyzing the hydrogen spectrum of nuclear magnetic resonance: after dissolving 1,3, 5-trimercaptomethylbenzene in deuterochloroform, a nuclear magnetic resonance hydrogen spectrum (figure 2) is obtained by testing, wherein delta is 1.77-1.81 ppm, delta is 3.69-3.71 ppm, delta is 7.16ppm, the number ratio of hydrogen of three chemical shifts is about 1: 2: 1, and the conclusion is drawn according to the size of the chemical shifts and the number ratio of hydrogen: δ -7.16 ppm corresponds to one hydrogen attached to the benzene ring at a in the trithiol molecule, and has a single peak due to the absence of hydrogen atoms on adjacent carbons; delta is 3.69-3.71 ppm and corresponds to two hydrogens on a methylene at the position b, and the double peak is formed under the influence that adjacent sulfur atoms are connected with one hydrogen; and delta is 1.77-1.81 ppm, corresponds to one hydrogen on the sulfydryl at the position c, and shows a triplet under the influence of two hydrogens on adjacent methylene groups.
Detecting and analyzing by nuclear magnetic resonance carbon spectrum: after 1,3, 5-trimercaptomethylbenzene is dissolved in deuterated chloroform, a nuclear magnetic resonance carbon spectrum (shown in figure 3) is obtained by testing, wherein delta is 76.89-77.53 ppm and is a solvent peak of the deuterated chloroform. The delta is 126.56ppm and corresponds to the carbon atom connected with hydrogen on the benzene ring at the position a in the molecule of the ternary mercaptan; 142.04ppm corresponds to the carbon atom linked to the methylene group on the benzene ring at b, and chemical shift is biased to low field by the influence of mercaptomethyl; δ 28.75ppm is at high field, corresponding to the carbon atom on the methylene at c.
The above comprehensive analysis proves that the target product 1,3, 5-trimercaptomethylbenzene is synthesized.
(2) Preparing a high-refractive-index optical resin lens: mixing 200g of 1,3, 5-trimercaptomethylbenzene trithiol with 280g of isocyanate compound, stirring, adding 3g of dibutyltin Dilaurate (DBTL) catalyst, then carrying out prepolymerization on the mixture at 60 ℃ for 40min, pouring the raw material into a mold after vacuum defoaming, heating the raw material to 120 ℃ according to a curing procedure to enable the raw material to be cured and molded, then slowly cooling to room temperature, demolding and cleaning to obtain the colorless transparent optical lens.
Example 2: preparation of 1,3, 5-trimercaptomethylbenzene and optical resin lens
(1) Preparation of 1,3, 5-trimercaptomethylbenzene: adding 40g of 1,3, 5-tribromomethylbenzene into a four-mouth bottle, adding 800mL of mixed solution of ethanol and n-butyl acetate, wherein the ethanol and the n-butyl acetate are prepared according to the mass ratio of 6: 1, stirring and dispersing uniformly by using magnetons, then adding 20g of thiourea, stirring for 24 hours, separating out a large amount of white precipitate, mixing the white precipitate with ethanol and the n-butyl acetate according to the mass ratio of 5: 1 by filtering, washing and filtering for 2-3 times, and drying to obtain white isothiourea salt; continuously adding 800mL of distilled water, stirring and dissolving until the solution is clear, then adding 20g of NaOH, heating and refluxing for 4 hours, and cooling to room temperature; cooling the system by using an ice bath, dropwise adding hydrochloric acid, adjusting the pH value of the system to 3, extracting by using 260mL multiplied by 3 of trichloromethane to obtain an organic phase solution containing the ternary mercaptan, and washing the organic phase solution to be neutral by using distilled water; stirring and adding 20g of attapulgite adsorbent into the trithiol after dehydration, stirring and mixing for 40 minutes, standing for 2.5 hours, adsorbing a small amount of azo chromophore in the solution, removing the attapulgite adsorbent at the lower layer by layers, and evaporating the solvent to obtain 15.2g of high-purity colorless 1,3, 5-trithiol methyl benzene.
The results of the infrared spectroscopy and the hydrogen nuclear magnetic resonance spectroscopy are similar to those of example 1.
(2) Preparing a high-refractive-index optical resin lens: mixing 200g of 1,3, 5-trimercaptomethylbenzene trithiol with 400g of isocyanate compound, stirring, adding 4g of dibutyltin Dilaurate (DBTL) catalyst, then carrying out prepolymerization on the mixture at 60 ℃ for 40min, pouring the raw material into a mold after vacuum deaeration, heating the raw material to 110 ℃ according to a curing procedure to enable the raw material to be cured and molded, then slowly cooling to room temperature, demolding and cleaning to obtain the colorless transparent optical lens.
Example 3: preparation of 1,3, 5-trimercaptomethylbenzene and optical resin lens
(1) Preparation of 1,3, 5-trimercaptomethylbenzene: adding 40g of 1,3, 5-tribromomethylbenzene into a four-mouth bottle, adding 1200mL of mixed solution of ethanol and n-butyl acetate, wherein the ethanol and the n-butyl acetate are prepared according to the mass ratio of 6: 1, stirring and dispersing uniformly by using magnetons, then adding 50g of thiourea, stirring for 24 hours, separating out a large amount of white precipitate, mixing the white precipitate with ethanol and the n-butyl acetate according to the mass ratio of 5: 1 by filtering, washing and filtering for 2-3 times, and drying to obtain white isothiourea salt; continuously adding 1200mL of distilled water, stirring and dissolving until the solution is clear, then adding 40g of NaOH, heating and refluxing for 5 hours, and cooling to room temperature; cooling the system by using an ice bath, dropwise adding hydrochloric acid, adjusting the pH value of the system to 3, extracting by using 400mL multiplied by 3 of trichloromethane to obtain an organic phase solution containing the ternary mercaptan, and washing the organic phase solution to be neutral by using distilled water; stirring and adding 50g of attapulgite adsorbent after dehydration, stirring and mixing for 40 minutes, standing for 2.5 hours, adsorbing a small amount of azo chromophore in the solution, removing the lower attapulgite adsorbent layer by layer, and evaporating the solvent to obtain 15.8g of high-purity colorless 1,3, 5-trimercapto methyl benzene.
The results of the infrared spectroscopy and the hydrogen nuclear magnetic resonance spectroscopy are similar to those of example 1.
(2) Preparing a high-refractive-index optical resin lens: mixing 200g of 1,3, 5-trimercaptomethylbenzene trithiol with 230g of isocyanate compound, stirring, adding 5g of dibutyltin Dilaurate (DBTL) catalyst, then carrying out prepolymerization on the mixture at 60 ℃ for 40min, pouring the raw material into a mold after vacuum deaeration, heating the raw material to 100 ℃ according to a curing procedure, curing and molding the raw material, then slowly cooling to room temperature, demolding and cleaning to obtain the colorless transparent optical lens.
Example 4: preparation of 1,3, 5-trimercaptomethylbenzene and optical resin lens
(1) Preparation of 1,3, 5-trimercaptomethylbenzene: adding 40g of 1,3, 5-tribromomethylbenzene into a four-mouth bottle, adding 900mL of mixed solution of ethanol and n-butyl acetate, wherein the ethanol and the n-butyl acetate are prepared according to the mass ratio of 6: 1, stirring and dispersing uniformly by using magnetons, then adding 26g of thiourea, stirring for 24 hours, separating out a large amount of white precipitate, mixing the white precipitate with ethanol and the n-butyl acetate according to the mass ratio of 5: 1 by filtering, washing and filtering for 2-3 times, and drying to obtain white isothiourea salt; continuously adding 900mL of distilled water, stirring and dissolving until the solution is clear, then adding 25g of NaOH, heating and refluxing for 4 hours, and cooling to room temperature; cooling the system by using an ice bath, dropwise adding hydrochloric acid, adjusting the pH value of the system to 3, extracting by using trichloromethane (280 mL multiplied by 3) to obtain an organic phase solution containing the ternary mercaptan, and washing the organic phase solution to be neutral by using distilled water; adding 26g of attapulgite adsorbent into the ternary mercaptan after dehydration, stirring and mixing for 40 minutes, standing for 2.5 hours, adsorbing a small amount of azo chromophore in the solution, removing the lower attapulgite adsorbent layer by layer, and evaporating the solvent to obtain the 15.5 high-purity colorless 1,3, 5-trimercapto methyl benzene.
The results of the infrared spectroscopy and the hydrogen nuclear magnetic resonance spectroscopy are similar to those of example 1.
(2) Preparing a high-refractive-index optical resin lens: mixing 200g of 1,3, 5-trimercaptomethylbenzene trithiol with 320g of isocyanate compound, stirring, adding 2g of dibutyltin Dilaurate (DBTL) catalyst, then carrying out prepolymerization on the mixture at 60 ℃ for 40min, pouring the raw material into a mold after vacuum defoaming, heating the raw material to 95 ℃ according to a curing procedure, carrying out curing molding on the raw material, then slowly cooling to room temperature, demolding and cleaning to obtain the colorless transparent optical lens.
Example 5: preparation of 1,3, 5-trimercaptomethylbenzene and optical resin lens
(1)1, 3, 5-trimercaptomethylbenzene: adding 40g of 1,3, 5-tribromomethylbenzene into a four-mouth bottle, adding 1100mL of mixed solution of ethanol and n-butyl acetate, wherein the ethanol and the n-butyl acetate are prepared according to the mass ratio of 6: 1, stirring and dispersing uniformly by using magnetons, then adding 40g of thiourea, stirring for 24 hours, separating out a large amount of white precipitate, mixing the white precipitate with ethanol and the n-butyl acetate according to the mass ratio of 5: 1 by filtering, washing and filtering for 2-3 times, and drying to obtain white isothiourea salt; continuously adding 1100mL of distilled water, stirring and dissolving until the solution is clear, then adding 35g of NaOH, heating and refluxing for 5 hours, and cooling to room temperature; cooling the system by using an ice bath, dropwise adding hydrochloric acid, adjusting the pH value of the system to 3, extracting with trichloromethane (350 mL multiplied by 3) to obtain an organic phase solution containing the ternary mercaptan, and washing the organic phase solution to be neutral by using distilled water; stirring and adding 40g of attapulgite adsorbent into the trithiol after dehydration, stirring and mixing for 40 minutes, standing for 2.5 hours, adsorbing a small amount of azo chromophore in the solution, removing the lower attapulgite adsorbent layer by layer, and evaporating the solvent to obtain 15.7g of high-purity colorless 1,3, 5-trithiol methyl benzene.
The results of the infrared spectroscopy and the hydrogen nuclear magnetic resonance spectroscopy are similar to those of example 1.
(2) Preparing a high-refractive-index optical resin lens: mixing 200g of 1,3, 5-trimercaptomethylbenzene trithiol with 200g of isocyanate compound, stirring, adding 5.5g of dibutyltin Dilaurate (DBTL) catalyst, then carrying out prepolymerization on the mixture at 60 ℃ for 40min, carrying out vacuum defoamation, pouring the raw material into a mold, heating the raw material to 120 ℃ according to a curing program, carrying out curing molding on the raw material, then slowly cooling to room temperature, demolding and cleaning to obtain the colorless transparent optical lens.
Comparative example 1: preparation of 1,3, 5-trithiol methyl benzene and optical resin lens by methanol solvent
(1) Preparation of 1,3, 5-trimercaptomethylbenzene: adding 40g of 1,3, 5-tribromomethylbenzene into a four-mouth bottle, adding 1000mL of methanol, stirring and dispersing magnetons uniformly, then adding 30g of thiourea, stirring for 24 hours until a large amount of white precipitate is separated out, filtering, washing and filtering for 2-3 times by using methanol, and drying to obtain white isothiourea salt; continuously adding 1000mL of distilled water, stirring and dissolving until the solution is clear, then adding 30g of NaOH, heating and refluxing for 4-5 hours, and cooling to room temperature; cooling the system by using an ice bath, dropwise adding hydrochloric acid, adjusting the pH value of the system to 3, extracting by using 300mL multiplied by 3 of trichloromethane to obtain an organic phase solution containing the ternary mercaptan, washing the organic phase solution to be neutral by using distilled water, drying by using anhydrous sodium sulfate, filtering, and carrying out rotary evaporation to obtain 19.2 g of 1,3, 5-trithiol methyl benzene.
(2) Preparing a high-refractive-index optical resin lens: mixing 200g of 1,3, 5-trimercaptomethylbenzene trithiol with 280g of isocyanate compound, stirring, adding 3g of dibutyltin Dilaurate (DBTL) catalyst, then carrying out prepolymerization on the mixture at 60 ℃ for 40min, pouring the raw material into a mold after vacuum defoaming, heating the raw material to 120 ℃ according to a curing procedure, curing and molding the raw material, then slowly cooling to room temperature, demolding and cleaning to obtain the colorless transparent optical lens.
Comparative example 2: preparation of 1,3, 5-trithiol methyl benzene and optical resin lens by ethanol solvent
(1) Preparation of 1,3, 5-trimercaptomethylbenzene: adding 40g of 1,3, 5-tribromomethylbenzene into a four-mouth bottle, adding 1000mL of ethanol, stirring and dispersing magnetons uniformly, then adding 30g of thiourea, stirring for 24 hours until a large amount of white precipitate is separated out, filtering, washing and filtering with ethanol for 2-3 times, and drying to obtain white isothiourea salt; continuously adding 1000mL of distilled water, stirring and dissolving until the solution is clear, then adding 30g of NaOH, heating and refluxing for 4-5 hours, and cooling to room temperature; cooling the system by using an ice bath, dropwise adding hydrochloric acid, adjusting the pH value of the system to 3, extracting by using 300mL multiplied by 3 of trichloromethane to obtain an organic phase solution containing the ternary mercaptan, washing the organic phase solution to be neutral by using distilled water, drying by using anhydrous sodium sulfate, filtering, and carrying out rotary evaporation to obtain 17.9g of 1,3, 5-trithiol methyl benzene.
(2) Preparing a high-refractive-index optical resin lens: mixing 200g of 1,3, 5-trimercaptomethylbenzene trithiol with 280g of isocyanate compound, stirring, adding 4g of dibutyltin Dilaurate (DBTL) catalyst, then carrying out prepolymerization on the mixture at 60 ℃ for 40min, pouring the raw material into a mold after vacuum defoaming, heating the raw material to 115 ℃ according to a curing procedure, curing and molding the raw material, then slowly cooling to room temperature, demolding and cleaning to obtain the colorless transparent optical lens.
Example 6
The optical properties of the samples prepared in examples 1-5 and comparative examples 1-2 were measured, wherein the transmittance was measured by using a UV-8000 model UV-VIS photometer from Shanghai chromatography Instrument Co., Ltd, and the measurement method was as follows: directly coating the resin monomer on a prism of an ultraviolet-visible light photometer to measure the light transmittance; the refractive index and Abbe number detection adopts a WZS1 Abbe refractometer of Shanghai optical instruments and equipments Limited company, and the detection method comprises the following steps: directly coating the resin monomer on a prism of an Abbe refractometer to measure the refractive index and the Abbe number; the yellow index is calculated from the reading of the spectrophotometer according to a formula.
The formula:
in the formula, YI is a yellow index; x, Y, Z is the tristimulus value of the C light source; and (3) surface hardness detection: the surface hardness of the resin sample was expressed by pencil hardness, and with reference to the national standard, a chinese high grade drawing pencil was used, the diameter of the lead was 1mm, the tip of the pencil was ground flat, and the pencil was pushed forward at 45 ℃ with a force of 1kg during the test, and the pencil hardness of the maximum hardness without scratches was used as the surface hardness of the sample. The results are shown in the following tables (Table I, Table II).
From the detection results, it is known that: the light transmittance of the 1,3, 5-trithiol methylbenzene prepared by the method is more than or equal to 89%, the refractive index is more than or equal to 1.65, and the yellow index is less than or equal to 1; the light transmittance of the lens is more than or equal to 90 percent, the refractive index is more than or equal to 1.66, and the yellow index is less than or equal to 1.50.
Table shows the results of measuring the optical properties of the ternary thiol monomers of the examples and the comparative examples
Table two examples and comparative examples optical lens performance test results
| Sample (I) | Transmittance (T%) | Refractive index (nd) | Yellow Index (YI) | Surface hardness (H) |
| Example 1 | 90.2 | 1.664 | 1.27 | 3H |
| Example 2 | 90.2 | 1.660 | 1.29 | 3H |
| Example 3 | 90.1 | 1.663 | 1.47 | 3H |
| Example 4 | 90.3 | 1.662 | 1.35 | 3H |
| Example 5 | 90.2 | 1.664 | 1.42 | 3H |
| Comparative example 1 | 88.6 | 1.641 | 2.19 | 3H |
| Comparative example 2 | 89.4 | 1.659 | 2.06 | 3H |
Claims (7)
1. A method for preparing a sulfur-containing optical resin material with high transmittance and high refractive index is characterized by comprising the following steps:
I. preparation of isothiourea salts: adding a mixed solvent of 1,3, 5-tribromomethylbenzene and ethanol-n-butyl acetate into a reaction vessel, and stirring and uniformly dispersing at room temperature; wherein the ethanol and the n-butyl acetate are mixed according to the mass ratio of (5.5-6.5) to 1, and the mass ratio of the 1,3, 5-tribromomethylbenzene to the mixed solvent is 1 to (20-30); then adding thiourea, stirring for 20-24 hours, wherein the mass ratio of the thiourea to the 1,3, 5-tribromomethylbenzene is (0.5-1.2) to 1, and a large amount of white precipitates are separated out from the solution; filtering, washing the precipitate with ethanol-n-butyl acetate mixed solution, filtering for 2-3 times, mixing ethanol and n-butyl acetate in the ethanol-n-butyl acetate mixed solution at a mass ratio of (4.5-5.5) to 1, and drying to obtain white isothiourea salt;
II, adding alkali for hydrolysis: adding isothiourea salt into distilled water with the weight of 20-30 times, stirring and dissolving until the solution is clear, adding sodium hydroxide flake caustic soda, heating and refluxing for 4-5 hours, and cooling to room temperature, wherein the mass ratio of the sodium hydroxide to the 1,3, 5-tribromomethylbenzene used in the step I is (0.5-1) to 1;
acidification to generate thiols: cooling the system to 10-20 ℃ by using an ice bath, dropwise adding hydrochloric acid to adjust the pH value of the system to 3-3.5, extracting by using trichloromethane to obtain an organic phase solution containing the ternary mercaptan, and washing the organic phase solution to be neutral by using distilled water;
and IV, decoloring and purifying: drying the solution obtained in the step III to remove water, adding an attapulgite adsorbent into the solution, wherein the particle size of the attapulgite adsorbent is 100-400 meshes, the adding amount of the adsorbent and the thiourea used in the step I are equal in mass, stirring and mixing for 35-45 minutes, standing for 2-3 hours, adsorbing a small amount of azo chromophores in the solution, removing the attapulgite adsorbent, and evaporating to remove the solvent to obtain high-purity colorless 1,3, 5-trimercapto methyl benzene;
v, curing reaction: and (3) taking dibutyltin dilaurate as a catalyst, and carrying out curing reaction on the 1,3, 5-trithiol methylbenzene obtained in the step IV and isocyanate to prepare the sulfur-containing optical resin material with high transmittance and high refractive index.
2. The preparation method according to claim 1, wherein the specific operation of step V is: mixing 1,3, 5-trimercapto methyl benzene and isocyanate compounds according to the molar ratio of (0.7-1.3) to (1-2); adding a catalyst dibutyltin dilaurate accounting for 1-3 wt% of 1,3, 5-trimercaptomethyl benzene, adding an auxiliary agent, then carrying out prepolymerization on the mixture at 58-62 ℃ for 35-45min, pouring the raw material into a mold after vacuum deaeration, heating the raw material to 90-130 ℃ for curing and molding, then slowly cooling to room temperature, demolding and cleaning to obtain the colorless transparent optical resin material.
3. The preparation method according to claim 2, wherein the molar ratio of the 1,3, 5-trimercaptomethylbenzene to the isocyanate compound is (0.7-1): (1-1.5).
4. The method according to any one of claims 1 to 3, wherein the isocyanate compound is one or a mixture of more than one of toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, 1, 6-hexamethylene diisocyanate, m-xylylene diisocyanate, naphthalene-1, 5-diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, and isophorone diisocyanate.
5. Preparation process according to claim 1, characterized in that it comprises the following operative steps:
I. preparation of isothiourea salts: adding a mixed solvent of 1,3, 5-tribromomethylbenzene and ethanol-n-butyl acetate into a reaction vessel, and stirring and uniformly dispersing at room temperature; wherein ethanol and n-butyl acetate are mixed according to the mass ratio of 6: 1, and the mass ratio of the 1,3, 5-tribromomethylbenzene to the mixed solvent is 1: 25; then adding thiourea, stirring for 24 hours, wherein the mass ratio of the thiourea to the 1,3, 5-tribromomethylbenzene is 3: 4, and a large amount of white precipitates are separated out from the solution; filtering, washing the precipitate with ethanol-n-butyl acetate mixed solution, filtering for 3 times, mixing ethanol and n-butyl acetate in the ethanol-n-butyl acetate mixed solution at a mass ratio of 5: 1, and drying to obtain white isothiourea salt;
II, adding alkali for hydrolysis: adding isothiourea salt into distilled water with the weight of 25 times, stirring and dissolving until the solution is clear, adding sodium hydroxide flake alkali, wherein the mass ratio of sodium hydroxide to the 1,3, 5-tribromomethylbenzene used in the step I is 3: 4, heating and refluxing for 5 hours, and cooling to room temperature;
acidification to generate thiols: cooling the system to below 20 ℃ by using an ice bath, dropwise adding hydrochloric acid to adjust the pH value of the system to 3, extracting by using trichloromethane to obtain an organic phase solution containing the ternary mercaptan, and washing the organic phase solution to be neutral by using distilled water;
and IV, decoloring and purifying: drying the solution obtained in the step III to remove water, adding an attapulgite adsorbent, wherein the addition amount of the adsorbent is equal to the mass of thiourea used in the step I, stirring and mixing for 40 minutes, standing for 2.5 hours, adsorbing a small amount of azo chromophore in the solution, removing the attapulgite adsorbent, and evaporating to remove the solvent to obtain high-purity colorless 1,3, 5-trimercapto methylbenzene;
v, curing reaction: mixing 1,3, 5-trimercapto methyl benzene and isocyanate compounds according to the molar ratio of (0.7-1) to (1-1.5); adding a catalyst dibutyltin dilaurate accounting for 1-3 wt% of 1,3, 5-trimercaptomethyl benzene, adding an auxiliary agent, then carrying out prepolymerization on the mixture at 60 ℃ for 40min, pouring the raw material into a mold after vacuum defoaming, heating the raw material to 90-130 ℃ to solidify and mold the raw material, then slowly cooling to room temperature, demolding and cleaning to obtain the colorless transparent optical resin material.
6. A high-transmittance, high-refractive-index sulfur-containing optical resin material, which is produced by the method according to any one of claims 1 to 5.
7. A high transmittance, high refractive index sulfur-containing optical resin lens produced by the method according to any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611151468.6A CN107200846B (en) | 2016-12-13 | 2016-12-13 | Sulfur-containing optical resin material with high transmittance and high refractive index and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611151468.6A CN107200846B (en) | 2016-12-13 | 2016-12-13 | Sulfur-containing optical resin material with high transmittance and high refractive index and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107200846A CN107200846A (en) | 2017-09-26 |
| CN107200846B true CN107200846B (en) | 2020-02-21 |
Family
ID=59904710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611151468.6A Active CN107200846B (en) | 2016-12-13 | 2016-12-13 | Sulfur-containing optical resin material with high transmittance and high refractive index and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107200846B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112300361B (en) * | 2019-07-29 | 2021-12-14 | 万华化学集团股份有限公司 | Preparation method and application of polyurethane optical resin |
| CN113461658B (en) * | 2021-06-15 | 2022-07-01 | 深圳市勇泰运科技有限公司 | High-refraction high-temperature-resistant optical monomer, optical resin and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329298A (en) * | 2011-07-22 | 2012-01-25 | 镇江俊视光学有限公司 | Optical resin monomer with high refractive index and preparation method thereof |
| CN105777596A (en) * | 2016-04-27 | 2016-07-20 | 江苏视客新材料股份有限公司 | Polyurethane type high-refraction optical resin monomer containing sulfur and preparation method of polyurethane type high-refraction optical resin monomer |
-
2016
- 2016-12-13 CN CN201611151468.6A patent/CN107200846B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329298A (en) * | 2011-07-22 | 2012-01-25 | 镇江俊视光学有限公司 | Optical resin monomer with high refractive index and preparation method thereof |
| CN105777596A (en) * | 2016-04-27 | 2016-07-20 | 江苏视客新材料股份有限公司 | Polyurethane type high-refraction optical resin monomer containing sulfur and preparation method of polyurethane type high-refraction optical resin monomer |
Non-Patent Citations (1)
| Title |
|---|
| 高折射率含硫树脂关键单体的设计、合成及性能研究;潘敏;《中国优秀硕士论文全文数据库 工程科技I辑》;20130715;第11页3-7行，第21页，第23页，表1.2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107200846A (en) | 2017-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10858473B2 (en) | Polythiol composition, polymerizable composition for optical material and use thereof | |
| EP0273661B1 (en) | Thiolcarboxylic acid esters | |
| KR0133656B1 (en) | Polythiol compound and optical material and products | |
| CN105777596B (en) | High refraction sulfur-bearing optical resin monomer of a kind of polyurethane-type and preparation method thereof | |
| CA2502710A1 (en) | Sulfide-containing polythiols | |
| CN107200846B (en) | Sulfur-containing optical resin material with high transmittance and high refractive index and preparation method thereof | |
| CN102329298B (en) | Optical resin monomer with high refractive index and preparation method thereof | |
| CN106279289B (en) | A kind of sulfur-containing epoxy resin monomer, optical resin material and preparation method thereof | |
| TWI570112B (en) | Preparation of bis (β-epoxypropyl) sulfide and bis (β-epoxypropyl) polysulfide | |
| US10207987B2 (en) | Polythiol composition and method for producing same | |
| CN107200847B (en) | High-refractive-index and high-hardness sulfur-containing optical resin material and preparation method thereof | |
| CN107188882B (en) | 1,3, 5-tricyclic thiopropyl mercaptomethylbenzene compound and preparation method thereof | |
| CN107188836B (en) | Tri- thiopurine methyltransferase benzene compound of 1,3,5- and preparation method thereof | |
| US20240034829A1 (en) | Polythiol composition, optical composition, and optical product | |
| CN105949096B (en) | The post-processing approach of optical glasses sheet material, refined multi-thiol and multi-thiol crude product | |
| CN116457385A (en) | Polythiol composition, optical composition and optical product | |
| CN114014789B (en) | Sulfur-containing high refractive index monomer and application thereof | |
| US20230357484A1 (en) | Polythiol composition and optical composition comprising same | |
| CN109053507B (en) | Polythiol compound for optical resin material and preparation method thereof | |
| CN116813567A (en) | Novel sulfur-containing high-refraction curable monomer | |
| CN112480095B (en) | Preparation method of bis (2, 3-thiocyclopropyl) sulfide | |
| US20240002336A1 (en) | Polythiol composition, optical composition, and optical product | |
| KR102034214B1 (en) | Method for preparing polythiol having improved storage stability | |
| CN111548340A (en) | Method for purifying episulfide compound | |
| CN116390965A (en) | Polythiol composition, optical composition and optical product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20190626 Address after: 211600 R&D Building, 73 Lishi Avenue, Jinhu Economic Development Zone, Huaian City, Jiangsu Province Applicant after: New material Limited by Share Ltd of Jiangsu University of optic science Address before: 211600 No. 73, Lishi Avenue, Jinhu Economic Development Zone, Huaian, Jiangsu Applicant before: Jiangsu Huatiantong Technology Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |