CN107200847B - High-refractive-index and high-hardness sulfur-containing optical resin material and preparation method thereof - Google Patents
High-refractive-index and high-hardness sulfur-containing optical resin material and preparation method thereof Download PDFInfo
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Abstract
A sulfur-containing optical resin material with high refractive index and high hardness and a preparation method thereof are disclosed, the preparation method comprises the following steps: reacting 1, 3, 5-tris (epoxypropyl) mercaptomethylbenzene with thiocyanide, extracting with trichloromethane by using a mixed solvent of ethanol, dichloromethane and water as a reaction solvent, and adsorbing impurities by using attapulgite to obtain high-purity colorless 1, 3, 5-tris (epoxypropyl) mercaptomethylbenzene; 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene and ternary mercaptan are subjected to polymerization reaction to prepare the sulfur-containing optical resin material with high refractive index and high hardness. The 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene 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-tricyclic thiopropyl mercaptomethylbenzene 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 sulfur-containing resin monomer with high transmittance and high refractive index, in particular to a preparation method of 1, 3, 5-tricyclopropylthiol methyl benzene, which is subjected to curing reaction with ternary mercaptan to prepare a sulfur-containing resin material with high transmittance and high refractive index.
Background
The sulfur element is usually in the form of thioether, thioester, sulfone group and the like in the polymer, and also exists in the form of episulfide and is polymerized by the episulfide group, so that the sulfur content of the polymer is remarkably improved.
Disclosure of Invention
The invention prepares the sulfur-containing optical resin material with high refractive index and high hardness and the lens by preparing the 1, 3, 5-tricyclopropylthiol methyl benzene monomer and carrying out polymerization addition reaction with the ternary mercaptan. The product prepared by the method has high refractive index, hardness and light transmittance and low yellow index.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for preparing a high-refractive-index, high-hardness sulfur-containing optical resin material, comprising the steps of:
I. ring opening and ring closing reaction: adding 1, 3, 5-tris (epoxypropyl) mercaptomethylbenzene, thiocyanide and a mixed solvent into a reactor, stirring and dissolving at 55-60 ℃, and continuously stirring for 4-5 hours to obtain 1, 3, 5-tris (epoxypropyl) mercaptomethylbenzene; wherein the mixed solvent consists of C1-C3 monohydric alcohol, dichloromethane and water, and the mass ratio of the 1, 3, 5-triethoxypropylmercaptomethylbenzene, the thiocyanide and the mixed solvent is 1: 2-5: 15-25;
II, extraction and separation: extracting the mixture obtained in the step I by using trichloromethane, washing an organic phase by using water, drying and distilling to obtain a light yellow transparent liquid;
III, decoloring and purifying: adding trichloromethane and an attapulgite adsorbent into 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene, wherein the mass ratio of the trichloromethane to the adsorbent to the 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene is (3-5) to (3-10) to 100, heating to 40-50 ℃, stirring and mixing for 15-20 minutes, standing for 2-2.5 hours, adsorbing a small amount of impurity chromophores in the solution, and filtering in a layered manner to remove the attapulgite adsorbent and the trichloromethane on the lower layer to finally obtain colorless and transparent 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene;
VI, curing reaction: 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene and ternary mercaptan are subjected to a curing reaction to prepare the sulfur-containing optical resin material with high refractive index and high hardness.
In the above preparation method, preferably, the thiocyanide is sodium thiocyanate, potassium thiocyanate or amine thiocyanate.
In the preparation method, the weight ratio of the C1-C3 monohydric alcohol to the dichloromethane to the water is preferably 2: 1.5-2.5: 0.8-1.5.
In the preparation method, the C1-C3 monohydric alcohol is at least one of methanol, ethanol and isopropanol.
In the above preparation method, the particle size of the attapulgite adsorbent is preferably 100 to 400 meshes.
In the preparation method described above, preferably, the specific operation of step VI is as follows: uniformly mixing the 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene and the ternary thiol compound according to the mass ratio of 100: 6-25, vacuumizing and degassing at 35-40 ℃ until no bubbles exist, injecting into a mold, curing in a curing furnace at 45-50 ℃ for 2-3 hours, heating to 100-120 ℃ at 10-15 ℃/20min for curing for 3-4 hours, naturally cooling to room temperature, and demolding to obtain the colorless transparent resin material.
In the preparation method, the trithiol is preferably 1, 3, 5-trimercaptomethylbenzene.
The preparation method as described above, preferably, the method comprises the following operation steps:
I. ring opening and ring closing reaction: adding 1, 3, 5-triethylene-oxypropyl mercaptomethylbenzene, thiocyanide and a mixed solvent into a reactor, stirring and dissolving at 56 ℃, and continuously stirring for 4-5 hours to obtain 1, 3, 5-tricyclopropyl mercaptomethylbenzene; wherein the mixed solvent consists of ethanol, dichloromethane and water, and the mass ratio of the 1, 3, 5-triethoxypropylmercaptomethylbenzene, the thiocyanide and the mixed solvent is 1: 3.2: 21;
II, extraction and separation: extracting the mixture obtained in the step I by using trichloromethane, washing an organic phase by using water, drying and distilling to obtain a light yellow transparent liquid;
III, decoloring and purifying: adding trichloromethane and an attapulgite adsorbent into 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene, wherein the mass ratio of the trichloromethane to the adsorbent to the 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene is (3-5) to (3-10) to 100, heating to 45 ℃, stirring and mixing for 15 minutes, standing for 2.5 hours, adsorbing a small amount of impurity chromophores in the solution, and filtering in layers to remove the lower attapulgite adsorbent and the trichloromethane to finally obtain colorless and transparent 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene;
VI, curing reaction: uniformly mixing 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene and 1, 3, 5-trimercaptomethylbenzene according to the mass ratio of 100: 16, vacuumizing and degassing at 40 ℃ until no bubbles exist, injecting into a mold, curing for 2 hours in a curing furnace at 50 ℃, then heating to 100 ℃ at 10 ℃/20min for curing for 3 hours, naturally cooling to room temperature, and demolding to obtain the colorless transparent resin material.
In another aspect, the present invention provides a high refractive index, high hardness sulfur-containing optical resin material prepared by the method as described above.
In yet another aspect, the present invention provides a high refractive index, high hardness sulfur-containing optical resin lens prepared by the method as described above.
The synthetic route of the 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene is as follows: the epoxy compound is subjected to ring opening under the action of thiocyanate ions, then forms a carbon-oxygen-sulfur five-membered ring through electron transfer, further opens the ring to exchange oxygen and sulfur positions, and finally closes the ring to obtain the 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene, wherein the specific reaction formula is as follows:
the raw material 1, 3, 5-tri-epoxypropyl mercaptomethylbenzene is slightly soluble in alcohol solvent and insoluble in water, three mixed solvents of alcohol solvent, dichloromethane and water are selected as reaction solvents, so that the reaction can be carried out in a homogeneous phase, and the reaction is facilitated.
The invention selects 1, 3, 5-trithiol methyl benzene as curing agent, the sulfydryl reacts with the episulfide group, two isomers (as the following formula) containing sulfydryl are generated after ring opening, the generated sulfydryl continuously reacts with the episulfide group, and the monomer and the curing agent are all three branched chains, and are continuously reacted and mutually cross-linked to be cured and molded.
In the synthesis method of the 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene monomer, thiocyanide is selected as a vulcanizing agent, three mixed solvents of ethanol, dichloromethane and water are used as reaction solvents, the speed of converting epoxy groups into episulfide groups is accelerated by controlling acid concentration, reaction temperature and reaction time, the whole reaction adopts a medium-low temperature reaction route and is carried out in a homogeneous phase mode, although by-products are increased due to the reaction temperature condition, the products are yellowed, but the whole reaction time is greatly shortened; meanwhile, after the product is decolorized by physical adsorption, the purity is high and the yellowness index is low.
The method has the beneficial effects that the 1, 3, 5-tricyclopropylthiocarbylbenzene prepared by the method has high light transmittance, refractive index and low yellowness index; the resin material prepared by the curing reaction of the modified epoxy resin and 1, 3, 5-trithiol methyl benzene has high light transmittance, high refractive index and low yellow index. Wherein, the transmittance of the 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene is more than or equal to 87 percent, the refractive index is more than or equal to 1.66, and the yellow index is less than or equal to 1.0; the light transmittance of the resin material is more than or equal to 88 percent, the refractive index is more than or equal to 1.68, the yellow index is less than or equal to 1.65, and the surface hardness is 4H.
Drawings
FIG. 1 is a FT-IR infrared spectrum of 1, 3, 5-tricyclopropylthiocarbylbenzene prepared in example 1.
FIG. 2 is a HNMR NMR spectrum of 1, 3, 5-tricyclopropylthiocarbylbenzene prepared in example 1.
FIG. 3 is a CNMR NMR carbon spectrum of 1, 3, 5-tricyclopropylthiocarbylbenzene prepared in example 1.
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: preparing 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene and resin lenses.
(1) Preparation of 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene: 50g of 1, 3, 5-tris-epoxypropyl mercaptomethylbenzene, 160g of potassium thiocyanate, 400g of ethanol, 400g of dichloromethane and 250g of water were added to a glass container, and the mixture was dissolved by stirring at 56 ℃ and stirred for about 5 hours. Then extracting with trichloromethane of 800g multiplied by 3, washing the collected organic phase for 3 times, drying with anhydrous sodium sulfate, filtering and rotary evaporating to obtain light yellow 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene liquid. Adding 1.8g of trichloromethane and 4.0g of attapulgite adsorbent, heating to 45 ℃, stirring and mixing for 15 minutes, standing for 2.5 hours, filtering to remove the lower attapulgite adsorbent and the trichloromethane, and finally obtaining 43.2g of colorless transparent 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene.
Infrared spectrum analysis: the obtained 1, 3, 5-tricyclopropylthiomethylbenzene is subjected to infrared spectrum detection (figure 1), and when the infrared spectrum of the 1, 3, 5-tricyclopropylthiomethylbenzene is compared with that of the 1, 3, 5-tricyclopropylthiomethylbenzene, the stretching vibration of an epoxy ring is 1242.95cm-1，837.49cm-1The absorption peak at (A) has disappeared, indicating that the epoxy ring has been completely converted, 3049.45cm-1Having absorption peaks in the C-H ringStretching vibration, 2916.63cm-1The nearby absorption peak is stretching vibration of methylene, 613.07cm-1The absorption peak is the stretching vibration of the episulfide ring.
Hydrogen nuclear magnetic resonance spectroscopy: subjecting the obtained 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene to nuclear magnetic resonance hydrogen spectrum detection (figure 2), wherein delta is 2.16-2.17 ppm, delta is 2.44-2.51 ppm, delta is 2.87-2.91 ppm, delta is 2.96-3.02 ppm, delta is 3.76-3.83ppm, delta is 7.21ppm, and the number ratio of six chemical shift hydrogens is approximately 1: 2: 1: 2: 1, and is deduced according to the size of chemical shift and the number ratio of hydrogens: delta is 2.16-2.17 ppm, delta is 2.44-2.51 ppm and corresponds to two hydrogens of methylene in an episulfide ring at a and one hydrogen of methine in an episulfide ring at b in a molecule of 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene, the chemical environment of the two hydrogens of the methylene at a is not equivalent, two peaks appear, one of the two peaks overlaps with the peak of the hydrogen at b, and the peaks are multiple; delta is 2.87-2.91 ppm, delta is 2.96-3.02 ppm corresponding to two hydrogens on a methylene connected with an episulfide ring at the position c, and the chemical environment of the two hydrogens on the methylene is not equivalent due to the fact that sulfur atoms on a chain cannot rotate freely, two peaks appear, and the peaks are also multiple; delta-3.76-3.83 ppm corresponds to two hydrogens on the methylene group connected with the benzene ring at d, and shows multiple peaks under the influence of a terminal group of the episulfide ring; and delta 7.21ppm corresponds to a hydrogen attached to the benzene ring at e, and no hydrogen atoms are present on adjacent carbons, thus showing a single peak.
Nuclear magnetic resonance carbon spectrum analysis: after 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene is dissolved in deuterated chloroform, a nuclear magnetic resonance carbon spectrum (shown in figure 3) is obtained through testing, wherein delta-76.82-77.46 ppm is a solvent peak of the deuterated chloroform. 25.90ppm corresponds to the carbon atom of the methylene in the episulfide ring at a in the molecule of the 1, 3, 5-tricyclopropylthiocypropylmercaptomethylbenzene; δ 33.85ppm corresponds to the carbon atom of the methine group in the episulfide ring at b; δ -37.76 ppm corresponds to the carbon atom of the methylene group attached to the episulfide ring at c; 5-36.52 ppm corresponds to the carbon atom of the methylene group at d which is attached to the benzene ring; δ 138.96ppm corresponds to the carbon atom on the phenyl ring at e which is attached to the methylene group; and delta-128.28 ppm corresponds to the carbon atom on the phenyl ring to which the hydrogen atom is attached at f.
The comprehensive analysis proves that the target product 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene is synthesized.
(2) Preparing a resin lens: uniformly mixing 50g of 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene and 8g of 1, 3, 5-trimercaptomethylthio benzenethiol, vacuumizing and degassing at 40 ℃ until no bubbles exist, injecting the mixture into a toughened glass mold, curing the mixture for 2 hours in a 50 ℃ curing furnace, heating the mixture to 100 ℃ at the temperature of 10 ℃/20min for curing for 3 hours, naturally cooling the mixture to room temperature, and demolding to obtain the colorless transparent resin lens.
Example 2: preparation of 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene and resin lens
(1) Preparation of 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene: 50g of 1, 3, 5-tris-epoxypropyl mercaptomethylbenzene, 110g of potassium thiocyanate, 300g of ethanol, 300g of dichloromethane and 160g of water were added to a glass container, and the mixture was dissolved by stirring at 56 ℃ and stirred for about 5 hours. Extracting with trichloromethane 650g multiplied by 3, washing the collected organic phase for 3 times, drying with anhydrous sodium sulfate, filtering, performing rotary evaporation to obtain a light yellow 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene liquid, adding 1.5g of trichloromethane and 2.5g of attapulgite adsorbent, heating to 45 ℃, stirring and mixing for 15 minutes, standing for 2.5 hours, filtering to remove the lower attapulgite adsorbent and the trichloromethane, and finally obtaining 41.5g of colorless transparent 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene.
The analysis results of the infrared spectrum, the nuclear magnetic resonance hydrogen spectrum and the carbon spectrum are similar to those of the example 1.
(2) Preparing a resin lens: uniformly mixing 50g of 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene and 3g of 1, 3, 5-trimercaptomethylthio benzenethiol, vacuumizing and degassing at 40 ℃ until no bubbles exist, injecting the mixture into a toughened glass mold, curing the mixture for 2 hours in a 50 ℃ curing furnace, heating the mixture to 100 ℃ at the temperature of 10 ℃/20min for curing for 3 hours, naturally cooling the mixture to room temperature, and demolding to obtain the colorless transparent resin lens.
Example 3: preparation of 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene and resin lens
(1) Preparation of 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene: adding 50g of 1, 3, 5-tris-epoxypropyl mercaptomethylbenzene, 240g of sodium thiocyanate, 460g of methanol, 460g of dichloromethane and 280g of water into a glass container, stirring and dissolving at 58 ℃, continuously stirring for about 5 hours for sharing, extracting by using 900g multiplied by 3 of trichloromethane, washing the collected organic phase for 3 times, drying by using anhydrous sodium sulfate, filtering, performing rotary evaporation to obtain a light yellow 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene liquid, adding 2.0g of trichloromethane and 4.0g of attapulgite adsorbent, heating to 50 ℃, stirring and mixing for 15 minutes, standing for 2.5 hours, filtering to remove the attapulgite adsorbent and the trichloromethane at the lower layer, and finally obtaining 44.0g of colorless and transparent 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene.
The analysis results of the infrared spectrum, the nuclear magnetic resonance hydrogen spectrum and the carbon spectrum are similar to those of the example 1.
(2) Preparing a resin lens: uniformly mixing 50g of 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene and 12g of 1, 3, 5-trimercaptomethylthio benzenethiol, vacuumizing and degassing at 40 ℃ until no bubbles exist, injecting the mixture into a toughened glass mold, curing the mixture for 2 hours in a 50 ℃ curing furnace, heating the mixture to 100 ℃ at the temperature of 10 ℃/20min for curing for 3 hours, naturally cooling the mixture to room temperature, and demolding to obtain the colorless transparent resin lens.
Example 4: preparation of 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene and resin lens
(1) Preparation of 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene: 50g of 1, 3, 5-tris-epoxypropyl mercaptomethylbenzene, 130g of sodium thiocyanate, 350g of ethanol, 360g of dichloromethane and 180g of water were added to a glass container, and the mixture was dissolved by stirring at 56 ℃ and stirred for about 5 hours. Extracting with trichloromethane (800 g × 3), washing the collected organic phase with water for 3 times, drying with anhydrous sodium sulfate, filtering, rotary-steaming to obtain a light yellow 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene liquid, adding 1.8g of trichloromethane and 3.5g of attapulgite adsorbent, heating to 50 ℃, stirring and mixing for 15 minutes, standing for 2.5 hours, filtering to remove the lower attapulgite adsorbent and trichloromethane, and finally obtaining 42.2g of colorless transparent 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene.
The analysis results of the infrared spectrum, the nuclear magnetic resonance hydrogen spectrum and the carbon spectrum are similar to those of the example 1.
(2) Preparing a resin lens: uniformly mixing 50g of 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene and 6g of 1, 3, 5-trimercaptomethylthio benzenethiol, vacuumizing and degassing at 40 ℃ until no bubbles exist, injecting the mixture into a toughened glass mold, curing the mixture for 2 hours in a 50 ℃ curing furnace, heating the mixture to 100 ℃ at the temperature of 10 ℃/20min for curing for 3 hours, naturally cooling the mixture to room temperature, and demolding to obtain the colorless transparent resin lens.
Example 5: preparation of 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene and resin lens
(1) Preparation of 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene: 50g of 1, 3, 5-trisepoxypropylmercaptomethylbenzene, 200g of ammonium thiocyanate, 430g of methanol, 400g of dichloromethane and 230g of water were charged into a glass vessel, and dissolved by stirring at 60 ℃ for about 5 hours while continuing stirring. Extracting with trichloromethane (800 g × 3), washing the collected organic phase with water for 3 times, drying with anhydrous sodium sulfate, filtering, rotary-steaming to obtain a light yellow 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene liquid, adding 1.9g of trichloromethane and 3.0g of attapulgite adsorbent, heating to 50 ℃, stirring and mixing for 15 minutes, standing for 2.5 hours, filtering to remove the lower attapulgite adsorbent and trichloromethane, and finally obtaining 43.5g of colorless transparent 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene.
The analysis results of the infrared spectrum, the nuclear magnetic resonance hydrogen spectrum and the carbon spectrum are similar to those of the example 1.
(2) Preparing a resin lens: uniformly mixing 50g of 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene and 10g of 1, 3, 5-trimercaptomethylthio benzenethiol, vacuumizing and degassing at 40 ℃ until no bubbles exist, injecting the mixture into a toughened glass mold, curing the mixture for 2 hours in a 50 ℃ curing furnace, heating the mixture to 100 ℃ at the temperature of 10 ℃/20min for curing for 3 hours, naturally cooling the mixture to room temperature, and demolding to obtain the colorless transparent resin lens.
Example 6: optical property detection experiment for 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene
The optical properties of the 1, 3, 5-tricyclopropylthiocypropylmercaptomethylbenzenes prepared in examples 1 to 5 were respectively detected, wherein the transmittance was detected by using a UV-8000 type UV-visible spectrophotometer, manufactured by shanghai chromatography instruments ltd, and the detection method was as follows: directly coating the sample 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 sample 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. From the detection results, it is known that: the light transmittance of the 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene prepared by the invention is more than or equal to 87 percent, the refractive index is more than or equal to 1.66, and the yellow index is less than or equal to 1.0.
TABLE 11, 3, 5-TRICYCLOTHIOPROPYL SULPHIMETHYLBENZENE BENZENE OPTICAL PERFORMANCE DETECTION RESULTS
| Sample (I) | Transmittance (T%) | Refractive index (nd) | Yellow Index (YI) |
| Example 1 | 87.7 | 1.662 | 0.93 |
| Example 2 | 87.6 | 1.661 | 0.95 |
| Example 3 | 87.5 | 1.660 | 0.99 |
| Example 4 | 87.6 | 1.661 | 0.94 |
| Example 5 | 87.7 | 1.662 | 0.96 |
Example 7: resin lens performance detection experiment
The resin substrates prepared in examples 1 to 5 were respectively tested for properties such as transmittance, refractive index, and yellow index, and the test results are shown in table 2 below. Wherein, the surface hardness detection: the surface hardness of the resin sample was expressed as pencil hardness, and with reference to GB/T6739-1996, a Chinese high-grade drawing pencil was used, the diameter of the lead was 1mm, the tip 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.
From the detection results, it is known that: the resin substrate manufactured by the invention has the light transmittance of more than or equal to 88 percent, the refractive index of more than or equal to 1.68, the yellow index of less than or equal to 1.65 and the surface hardness of 4H.
TABLE 2 resin lens Performance test results
| Sample (I) | Transmittance (T%) | Refractive index (nd) | Yellow Index (YI) | Surface hardness (H) |
| Example 1 | 88.5 | 1.687 | 1.62 | 4H |
| Example 2 | 88.4 | 1.685 | 1.64 | 4H |
| Example 3 | 88.3 | 1.685 | 1.64 | 4H |
| Example 4 | 88.4 | 1.686 | 1.63 | 4H |
| Example 5 | 88.5 | 1.687 | 1.63 | 4H |
Claims (9)
1. A method for preparing a sulfur-containing optical resin material with high refractive index and high hardness is characterized by comprising the following steps:
I. ring opening and ring closing reaction: adding 1, 3, 5-tris (epoxypropyl) mercaptomethylbenzene, thiocyanide and a mixed solvent into a reactor, stirring and dissolving at 55-60 ℃, and continuously stirring for 4-5 hours to obtain 1, 3, 5-tris (epoxypropyl) mercaptomethylbenzene; wherein the thiocyanide is sodium thiocyanate, potassium thiocyanate or ammonium thiocyanate; the mixed solvent consists of C1-C3 monohydric alcohol, dichloromethane and water, and the mass ratio of the 1, 3, 5-triethoxypropylmercaptomethylbenzene, the thiocyanide and the mixed solvent is 1: 2-5: 15-25;
II, extraction and separation: extracting the mixture obtained in the step I by using trichloromethane, washing an organic phase by using water, drying and distilling to obtain a light yellow transparent liquid;
III, decoloring and purifying: adding trichloromethane and an attapulgite adsorbent into 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene, wherein the mass ratio of the trichloromethane to the adsorbent to the 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene is (3-5) to (3-10) to 100, heating to 40-50 ℃, stirring and mixing for 15-20 minutes, standing for 2-2.5 hours, adsorbing a small amount of impurity chromophores in the solution, and filtering in a layered manner to remove the attapulgite adsorbent and the trichloromethane on the lower layer to finally obtain colorless and transparent 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene;
VI, curing reaction: 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene and ternary mercaptan are subjected to a curing reaction to prepare the sulfur-containing optical resin material with high refractive index and high hardness.
2. The method of claim 1, wherein the weight ratio of the C1-C3 monohydric alcohol to the methylene chloride to the water is 2: 1.5-2.5: 0.8-1.5.
3. The method of claim 1, wherein the C1-C3 monohydric alcohol is at least one of methanol, ethanol, and isopropanol.
4. The preparation method according to claim 1, wherein the particle size of the attapulgite adsorbent is 100 to 400 mesh.
5. The preparation method according to claim 1, wherein the specific operation of step VI is as follows: uniformly mixing the 1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene and the ternary thiol compound according to the mass ratio of 100: 6-25, vacuumizing and degassing at 35-40 ℃ until no bubbles exist, injecting into a mold, curing in a curing furnace at 45-50 ℃ for 2-3 hours, heating to 100-120 ℃ at 10-15 ℃/20min for curing for 3-4 hours, naturally cooling to room temperature, and demolding to obtain the colorless transparent resin material.
6. The method according to claim 5, wherein the trithiol is 1, 3, 5-trimercaptomethylbenzene.
7. Preparation process according to claim 6, characterized in that it comprises the following operative steps:
I. ring opening and ring closing reaction: adding 1, 3, 5-triethylene-oxypropyl mercaptomethylbenzene, thiocyanide and a mixed solvent into a reactor, stirring and dissolving at 56 ℃, and continuously stirring for 4-5 hours to obtain 1, 3, 5-tricyclopropyl mercaptomethylbenzene; wherein the mixed solvent consists of ethanol, dichloromethane and water, and the mass ratio of the 1, 3, 5-triethoxypropylmercaptomethylbenzene, the thiocyanide and the mixed solvent is 1: 3.2: 21;
II, extraction and separation: extracting the mixture obtained in the step I by using trichloromethane, washing an organic phase by using water, drying and distilling to obtain a light yellow transparent liquid;
III, decoloring and purifying: adding trichloromethane and an attapulgite adsorbent into 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene, wherein the mass ratio of the trichloromethane to the adsorbent to the 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene is (3-5) to (3-10) to 100, heating to 45 ℃, stirring and mixing for 15 minutes, standing for 2.5 hours, adsorbing a small amount of impurity chromophores in the solution, and filtering in layers to remove the lower attapulgite adsorbent and the trichloromethane to finally obtain colorless and transparent 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene;
VI, curing reaction: uniformly mixing 1, 3, 5-tricyclothiopropyl mercaptomethylbenzene and 1, 3, 5-trimercaptomethylbenzene according to the mass ratio of 100: 16, vacuumizing and degassing at 40 ℃ until no bubbles exist, injecting into a mold, curing for 2 hours in a curing furnace at 50 ℃, then heating to 100 ℃ at 10 ℃/20min for curing for 3 hours, naturally cooling to room temperature, and demolding to obtain the colorless transparent resin material.
8. A high refractive index, high hardness sulfur-containing optical resin material, characterized in that it is produced by the method according to any one of claims 1 to 7.
9. A high refractive index, high hardness sulfur-containing optical resin lens produced by the method according to any one of claims 1 to 7.
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