CN107188882B - 1,3, 5-tricyclic thiopropyl mercaptomethylbenzene compound and preparation method thereof - Google Patents
1,3, 5-tricyclic thiopropyl mercaptomethylbenzene compound and preparation method thereof Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D331/00—Heterocyclic compounds containing rings of less than five members, having one sulfur atom as the only ring hetero atom
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- 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
- C08G75/06—Polythioethers from cyclic thioethers
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- 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
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Abstract
A1, 3, 5-tricyclic thiopropyl mercaptomethylbenzene compound and a preparation method thereof, wherein 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 the high-purity colorless 1,3, 5-tris (epoxypropyl) mercaptomethylbenzene. The 1,3, 5-tricyclic thiopropyl mercaptomethylbenzene compound prepared by the method has high purity, has the advantages of high refractive index, high transmittance and the like, and has the light transmittance of more than or equal to 89%, the refractive index of more than or equal to 1.65 and the yellow index of less than or equal to 1.
Description
Technical Field
The invention relates to a preparation method of an episulfide resin monomer with high transmittance and high refractive index, in particular to a preparation method of 1,3, 5-tricyclothiopropyl mercaptomethylbenzene.
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 provides a preparation method of an episulfide resin monomer with high transmittance and high refractive index, and particularly relates to a synthesis method of 1,3, 5-tricyclothiopropyl mercaptomethylbenzene.
In order to achieve the purpose, the invention provides the following technical scheme:
a process for preparing a 1,3, 5-tricyclopropylthiol methylbenzene compound, 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 at the lower layer to finally obtain colorless and transparent 1,3, 5-tricyclothiopropyl mercaptomethylbenzene.
The production method as described above, wherein the thiocyanide is sodium thiocyanate, potassium thiocyanate or amine thiocyanate.
The preparation method is characterized in that the weight ratio of the C1-C3 monohydric alcohol to the dichloromethane to the water is 2: 1.5-2.5: 0.8-1.5.
The preparation method is characterized in that the C1-C3 monohydric alcohol is at least one of methanol, ethanol and isopropanol.
The preparation method is characterized in that the particle size of the attapulgite adsorbent is 100-400 meshes.
The preparation process as described above, 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 5 hours to obtain 1,3, 5-triethylene-oxypropyl 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 a layered manner to remove the lower attapulgite adsorbent and the trichloromethane to finally obtain the colorless and transparent 1,3, 5-tricyclothiopropyl mercaptomethylbenzene.
In another aspect, the present invention provides a 1,3, 5-tricyclopropylthiol methylbenzene compound, which is prepared by the method as described above.
In another aspect, the present invention provides the use of the 1,3, 5-tricyclopropylthiocypropylmercaptomethylbenzene compound as described above for the preparation of high transmittance, high refractive optical resin lenses.
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.
1,3, 5-tri-epoxypropyl mercaptomethylbenzene and 1,3, 5-tri-mercaptomethylbenzene can be subjected to curing reaction to prepare the sulfur-containing optical resin material. The episulfide group reacts with the sulfhydryl group, two isomers (as shown in the following formula) containing the sulfhydryl group are generated after ring opening, the generated sulfhydryl group continuously reacts with the episulfide group, and the monomer and the curing agent are both three branched chains, and are continuously reacted and mutually crosslinked to be cured and molded.
The method has the beneficial effects that the method selects the thiocyanide as the vulcanizing agent, takes three mixed solvents of ethanol, dichloromethane and water as the reaction solvent, accelerates the speed of converting epoxy groups into episulfide groups by controlling acid concentration, reaction temperature and reaction time, adopts a medium-low temperature reaction route for the whole reaction, 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 1,3, 5-tricyclic thiopropyl mercaptomethylbenzene prepared by the method has high light transmittance, refractive index and low yellowness index, wherein the transmittance is more than or equal to 87 percent, the refractive index is more than or equal to 1.66, and the yellowness index is less than or equal to 1.0; the resin lens manufactured by using the compound as a monomer 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.
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) The preparation method comprises the steps of adding 50g of 1,3, 5-tricyclothiopropyl mercaptomethylbenzene, 160g of potassium thiocyanate, 400g of ethanol, 400g of dichloromethane and 250g of water into a glass container, stirring and dissolving at 56 ℃, continuously stirring for 5 hours for sharing, extracting with 800g of trichloromethane × 3, washing the collected organic phase for 3 times, drying with anhydrous sodium sulfate, filtering, performing rotary evaporation to obtain a yellowish 1,3, 5-tricyclothiopropyl 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 attapulgite adsorbent and the trichloromethane at the lower layer, and finally obtaining 43.2g of colorless and transparent 1,3, 5-tricyclothiopropyl 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-1The absorption peak is the stretching vibration of the benzene ring C-H, 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 atom is 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; δ -36.52 ppm corresponds to the carbon atom of the methylene group attached to the benzene ring at d; 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-tricyclic thiopropyl mercaptomethylbenzene and 8g of 1,3, 5-trimercaptomethyl benzenethiol, vacuumizing and degassing at 40 ℃ until no bubbles exist, injecting into a toughened glass mold, curing in a 50 ℃ curing furnace for 2 hours, heating to 100 ℃ for curing for 3 hours, naturally cooling 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) The preparation method comprises the steps of adding 50g of 1,3, 5-tricyclothiopropyl mercaptomethylbenzene, 110g of potassium thiocyanate, 300g of ethanol, 300g of dichloromethane and 160g of water into a glass container, stirring and dissolving at 56 ℃, continuously stirring for 5 hours for sharing, extracting with 650g of trichloromethane × 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 attapulgite adsorbent and the trichloromethane at the lower layer, and finally obtaining 41.5g of colorless and 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-tricyclic thiopropyl mercaptomethylbenzene and 3g of 1,3, 5-trimercaptomethyl benzenethiol, vacuumizing and degassing at 40 ℃ until no bubbles exist, injecting into a toughened glass mold, curing in a 50 ℃ curing furnace for 2 hours, heating to 100 ℃ for curing for 3 hours, naturally cooling 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) The preparation method of the 1,3, 5-tricyclic thiopropyl mercaptomethylbenzene comprises the steps of adding 50g of 1,3, 5-tricyclic thiopropyl 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 5 hours for sharing, extracting with 900g of trichloromethane × 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-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-tricyclic thiopropyl mercaptomethylbenzene and 12g of 1,3, 5-trimercaptomethyl benzenethiol, vacuumizing and degassing at 40 ℃ until no bubbles exist, injecting into a toughened glass mold, curing in a 50 ℃ curing furnace for 2 hours, heating to 100 ℃ for curing for 3 hours, naturally cooling 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) The preparation method of the 1,3, 5-tricyclic thiopropyl mercaptomethylbenzene comprises the steps of adding 50g of 1,3, 5-tricyclic thiopropyl mercaptomethylbenzene, 130g of sodium thiocyanate, 350g of ethanol, 360g of dichloromethane and 180g of water into a glass container, stirring and dissolving at 56 ℃, continuously stirring for 5 hours for sharing, extracting with 800g of trichloromethane × 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-tricyclic thiopropyl 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 attapulgite adsorbent and the trichloromethane at the lower layer, and finally obtaining 42.2g 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-tricyclic thiopropyl mercaptomethylbenzene and 6g of 1,3, 5-trimercaptomethyl benzenethiol, vacuumizing and degassing at 40 ℃ until no bubbles exist, injecting into a toughened glass mold, curing in a 50 ℃ curing furnace for 2 hours, heating to 100 ℃ for curing for 3 hours, naturally cooling 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) The preparation method of the 1,3, 5-tricyclic thiopropyl mercaptomethylbenzene comprises the steps of adding 50g of 1,3, 5-tricyclic thiopropyl mercaptomethylbenzene, 200g of ammonium thiocyanate, 430g of methanol, 400g of dichloromethane and 230g of water into a glass container, stirring and dissolving at 60 ℃, continuously stirring for 5 hours for sharing, extracting with 800g of trichloromethane × 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-tricyclic thiopropyl 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 attapulgite adsorbent and the trichloromethane at the lower layer, and finally obtaining 43.5g 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-tricyclic thiopropyl mercaptomethylbenzene and 10g of 1,3, 5-trimercaptomethyl benzenethiol, vacuumizing and degassing at 40 ℃ until no bubbles exist, injecting into a toughened glass mold, curing in a 50 ℃ curing furnace for 2 hours, heating to 100 ℃ for curing for 3 hours, naturally cooling 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 (5)
1. A method for preparing a 1,3, 5-tricyclopropylthiol methylbenzene compound, 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 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-tris-epoxypropyl mercaptomethylbenzene to the thiocyanide to 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 attapulgite adsorbent into 1,3, 5-tricyclic thiopropyl mercaptomethylbenzene, wherein the mass ratio of the trichloromethane to the adsorbent to the 1,3, 5-tricyclic thiopropyl mercaptomethylbenzene is (3-5): (3-10): 100, heating to 40-50 ℃, stirring and mixing for 15-20 minutes, standing for 2-2.5 hours, adsorbing a small amount of impurity chromophore in the solution, and filtering in a layered manner to remove the lower attapulgite adsorbent and the trichloromethane, thereby finally obtaining the colorless and transparent 1,3, 5-tricyclic thiopropyl mercaptomethylbenzene.
2. The method of claim 1, wherein the weight ratio of the C1-C3 monoalcohol, dichloromethane, and water is 2 (1.5-2.5) to (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. Preparation process according to claim 1, 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 5 hours to obtain 1,3, 5-triethylene-oxypropyl mercaptomethylbenzene; wherein the mixed solvent consists of ethanol, dichloromethane and water, and the mass ratio of the 1,3, 5-tris (epoxypropyl) mercaptomethylbenzene, 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): (3-10): 100, heating to 45 ℃, stirring and mixing for 15 minutes, standing for 2.5 hours, adsorbing a small amount of impurity chromophore in the solution, and filtering in a layered manner to remove the lower attapulgite adsorbent and the trichloromethane to finally obtain colorless and transparent 1,3, 5-tricyclothiopropyl mercaptomethylbenzene.
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| "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7期);B016-50 * |
| 潘敏."高折射率含硫树脂关键单体的设计、合成及性能研究".《中国优秀硕士论文全文数据库 工程科技I辑》.2013,(第7期),B016-50. * |
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