CN110776491B - Multi-branched thioether-type ring sulfur compound and preparation method and application thereof - Google Patents
Multi-branched thioether-type ring sulfur compound and preparation method and application thereof Download PDFInfo
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- CN110776491B CN110776491B CN201911178766.8A CN201911178766A CN110776491B CN 110776491 B CN110776491 B CN 110776491B CN 201911178766 A CN201911178766 A CN 201911178766A CN 110776491 B CN110776491 B CN 110776491B
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- C—CHEMISTRY; METALLURGY
- 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
- C07D331/02—Three-membered rings
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- 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
- C08G75/06—Polythioethers from cyclic thioethers
- C08G75/08—Polythioethers from cyclic thioethers from thiiranes
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- G—PHYSICS
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- 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
Abstract
The multi-branched thioether-type ring sulfur compound provided by the invention is prepared by a specific method, so that compared with the existing multi-branched thioether-type ring sulfur compound, the multi-branched thioether-type ring sulfur compound provided by the invention is used as a raw material of an optical material, the transparency, the refractive index and the heat resistance of the prepared optical material all meet the requirements of optical plastics required by market use, and the refractive index can reach more than 1.75, so that the multi-branched thioether-type ring sulfur compound is a plastic lens material with excellent performance and wide application prospect.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a multi-branched thioether-type ring sulfur compound and a preparation method and application thereof.
Background
In recent years, plastic lenses have been rapidly popularized in the fields of spectacle lenses, cameras, camera lenses, and the like, instead of conventional inorganic glass lenses, because of their advantages such as light weight, difficulty in breaking, and dyeability. At present, plastic lenses with low refractive index such as PC, PMMA, CR-39 and the like are widely used in the market, but further high performance including high refractive index, high abbe number, low specific gravity, high heat resistance and the like is required for resins used for plastic lenses.
Among them, in addition to polythiourethane materials (patent document 1) using polyisocyanates and polythiols as raw materials, resins synthesized using thioether-type ring sulfur compounds as monomers are also very drawing attention from domestic markets, have a high refractive index and a high abbe number (patent documents 2 and 3), and have a refractive index of 1.70 or more, and can satisfy the requirements of high myopia population for the material and performance of spectacles.
Patent document 1: CN101511895B
Patent document 2: CN106232658A
Patent document 3: WO2010131631A1
Disclosure of Invention
In view of the above, the present invention provides a multi-branched thioether-type cyclic sulfur compound, which is prepared by a specific method, so that the compound obtained by using the compound in an optical material can obtain a compound having an ultrahigh refractive index.
The invention provides a preparation method of a multi-branched thioether-type ring sulfur compound, which comprises the following steps:
1) reacting a compound shown in a formula (1) with thiourea under an acidic condition to generate isothiourea salt;
wherein R is a C1-C10 linear alkyl group, a C1-C10 branched alkyl group, a substituted aryl group or an unsubstituted aryl group, m is an integer of 0-4, and n is an integer of 2-4;
2) hydrolyzing isothiourea salt under alkaline conditions to obtain a compound shown as a formula (2);
3) reacting the compound shown in the formula (2) with epoxy chloropropane to obtain a compound shown in a formula (3);
4) converting the compound of formula (3) into a compound of formula (4);
preferably, the solvent for the reaction in step 1) is water;
the mass ratio of the sum of the mass of the compound shown in the formula (1) and the thiourea to the water is 1: 3.0-8.0.
The invention also provides a multi-branched thioether-type ring sulfur compound with a structure shown in a formula (4) prepared by the preparation method,
wherein R is C1-C10 linear alkyl, C1-C10 branched alkyl, substituted aryl or unsubstituted aryl,
m is an integer of 0 to 4,
n is an integer of 2 to 4.
Preferably, R is a linear alkyl group of C2-C6, a branched alkyl group of C2-C6, a substituted aryl group of C7-C15 or an unsubstituted aryl group of C6-C15.
Preferably, R is CH3-、-CH2-、
R1CH2-、
Phenyl, methylphenyl, halophenyl, naphthyl, anthryl, phenanthryl or fluorenyl;
wherein, R is1Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isopropyl, tert-butyl, n-pentyl, isopentyl, n-hexyl or phenyl.
Preferably, the structure of the formula (4) is specifically a structure of a formula (4-1) or a formula (4-2),
the invention also provides an optical material, which is obtained by mixing and curing the polymerizable composition;
wherein the polymerizable composition comprises: the multi-branched thioether-type cyclic sulfur compound, sulfur, polythiol and thioether according to any one of claims 3 to 6.
Preferably, the thioether is one or both of bis (β -epithiopropyl) sulfide and bis (β -epithiopropyl) disulfide.
Preferably, the polythiols are bis (mercaptoethyl) sulfide, 1, 3-bis (mercaptomethyl) benzene, 1, 3, 3-tetrakis (mercaptomethylthio) propane, 1, 2, 2-tetrakis (mercaptomethylthio) ethane, 2, 5-dimercaptomethyl-1, 4-dithiane, pentaerythritol tetrakis (3-mercaptopropionate), 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, and 5, 7-dimercaptomethyl-1, 11-dimercapto-3, one or more of 6, 9-trithioundecane.
Preferably, the polymerizable composition further comprises one or more of a polymerization catalyst, an internal mold release agent, a light stabilizer, a blue colorant, an ultraviolet absorber, an antioxidant and a dye.
Compared with the prior art, the multi-branched thioether-type ring sulfur compound provided by the invention is prepared by a specific method, so that compared with the existing multi-branched thioether-type ring sulfur compound, the multi-branched thioether-type ring sulfur compound is used as a raw material of an optical material, the transparency, the refractive index and the heat resistance of the prepared optical material all meet the requirements of optical plastics required by market use, the refractive index can reach more than 1.75, and the multi-branched thioether-type ring sulfur compound is a plastic lens material with excellent performance and wide application prospect.
Detailed Description
The invention provides a preparation method of a multi-branched thioether-type ring sulfur compound, which comprises the following steps:
1) reacting a compound shown as a formula (1) with thiourea under an acidic condition to generate isothiourea salt:
wherein R is a C1-C10 linear alkyl group, a C1-C10 branched alkyl group, a substituted aryl group or an unsubstituted aryl group, m is an integer of 0-4, and n is an integer of 2-4;
2) hydrolyzing isothiourea salt under alkaline conditions to obtain a compound shown as a formula (2);
3) reacting the compound shown in the formula (2) with epoxy chloropropane to obtain a compound shown in a formula (3);
4) converting the compound of formula (3) into a compound of formula (4);
according to the invention, the compound shown in the formula (1) reacts with thiourea under an acidic condition to generate isothiourea salt; the solvent for the reaction in the step 1) is water; the mass ratio of the sum of the mass of the compound represented by the formula (1) and thiourea to the water is preferably 1: 3.0-8.0, and more preferably 1: 5.0-7.0; the acid providing the acidic condition is preferably hydrochloric acid, wherein the usage amount of hydroxyl, thiourea and hydrochloric acid of the polyol compound with the structure shown in the formula (I) is 1 to (1-2), preferably 1 to (1-1.2) in molar ratio; the reaction temperature is 80-120 ℃, and preferably 105-115 ℃; the reaction time is 2-8 h, preferably 3-5 h.
According to the invention, the isothiourea salt is hydrolyzed under alkaline conditions to obtain the compound shown in the formula (2); wherein, the alkali providing the alkaline condition is one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, ammonia and ammonia gas, preferably sodium hydroxide, potassium hydroxide or ammonia, more preferably ammonia; the molar ratio of the alkali to the hydrochloric acid added in salifying is (1-3) to 1, preferably (1.1-2) to 1; the concentration of the ammonia water is 10-25%, and the preferable concentration is 16-25%.
In the present invention, it is preferable to further add an organic solvent before adding the alkali solution. The addition of the organic solvent simplifies the separation and post-treatment of the product, and the obtained plastic lens has good chromaticity, wherein the organic solvent is preferably one or more of toluene, xylene, chlorobenzene and dichlorobenzene, and is preferably toluene; the using amount is 0.2-3 times, preferably 0.2-1.5 times of the mass of the reaction liquid;
in the invention, in the alkaline hydrolysis reaction process, the temperature of a reaction system is maintained at 15-60 ℃, and preferably 30-55 ℃; the adding time of the alkali liquor is preferably 20-50 min; after the addition of the alkali liquor is finished, maintaining the temperature of the system within the range of 40-80 ℃, preferably 45-70 ℃; continuously reacting for 1-8 h, preferably 2-5 h; standing and layering after the alkaline hydrolysis reaction is finished, and cutting off the solvent to obtain the crude product of the branched polythiol compound with the structure shown in the formula (2).
In the invention, the obtained branched polythiol compound crude product is purified, and specifically, the crude product is subjected to acid washing and multiple times of water washing; or washing and purifying by the sequence of acid washing, water washing, alkali washing and water washing. Impurities can be removed efficiently through washing, and then the phenomena of white turbidity, vein and the like generated by the cured optical material are reduced, and the method that the crude product washing process is acid washing-water washing-alkali washing-water washing, water washing-acid washing-water washing-alkali washing-water washing or acid washing-water washing is preferred. Each washing step can be repeated for a plurality of times according to the impurity removal requirement. In the washing process, in order to avoid introducing other ions, hydrochloric acid is preferably used for pickling the polythiol crude product, and the concentration of the hydrochloric acid is 25-36%, preferably 30-36%; the washing temperature is 10-60 ℃, and preferably 30-55 ℃; in order to avoid the influence of oxygen on the product chromaticity, degassed water with the oxygen concentration of less than 7mg/L can be used for washing the crude product, so that the problems of color tone and turbidity in the plastic lens can be effectively inhibited; the alkali washing can be carried out by adding an alkaline aqueous solution, preferably an ammonia aqueous solution, wherein the concentration is 0.1-10%, preferably 0.1-1%;
in the invention, the mixture after washing treatment is subjected to removal and filtration of the solvent and the low boiling point compound; the removal of the solvent and the low boiling point compound may be carried out under normal pressure or reduced pressure, and depending on the solvent used, it is preferably carried out under reduced pressure at 100 ℃ or lower, more preferably under reduced pressure at 85 ℃ or lower, and this step may be carried out while introducing an inert gas such as nitrogen; the filtration is mainly for removing solid impurities such as salts, and can be carried out by filtration under reduced pressure or pressure using a membrane filter or a cartridge filter, and the pore size of the filter used is preferably 5 μm or less, preferably 2 μm or less, to obtain a purified polybranched thiol compound.
According to the invention, the compound shown in the formula (2) is reacted with epoxy chloropropane to obtain a compound shown in the formula (3); in order to enable the reaction to be carried out more smoothly, the invention preferably adds the alkali solution into the compound shown in the formula (2), and keeps the system temperature below 30 ℃ in the dropping process, wherein the dropping time is 10-50 min, preferably 20-30 min; the alkali in the added alkali solution can be sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, ammonia water or ammonia gas, and is preferably sodium hydroxide; the mass concentration of the sodium hydroxide is preferably 20-40%, and more preferably 25-32%; the usage amount is (0.5-3) to 1, preferably (0.95-1.5) to 1 in terms of the molar ratio of the sodium hydroxide to the-SH in the polythiol; after the alkali liquor is dripped, the temperature is kept for 20min, then epichlorohydrin is dripped into the system, the temperature of the dripping epichlorohydrin and the subsequent reaction is preferably 0-50 ℃, more preferably 5-25 ℃, and the temperature is kept for 20min after the reaction is finished; the molar ratio of the added epoxy chloropropane to-SH is (0.5-1.5): 1 based on the amount of thiol-group substances in the polythiol. Preferably (0.98-1.05) to 1.
According to the invention, the compound of formula (3) is also converted into the compound of formula (4), wherein the vulcanizing agent for conversion reaction is preferably thiourea, sodium thiocyanate, potassium thiocyanate or ammonium thiocyanate, more preferably thiourea; the amount of thiourea used is 1 to 5 equivalents, preferably 1 to 3 equivalents, based on the epoxy group in formula (3); the reaction temperature is 0-60 ℃, and preferably 10-40 ℃; the reaction time is 10-30 h, preferably 20-28 h; the conversion reaction is preferably carried out in a solvent, the reaction solvent is preferably one or more of dichloromethane, chloroform, dichloroethane, toluene, xylene, chlorobenzene, dichlorobenzene, nitrobenzene, methanol, ethanol, isopropanol, butanol, methoxyethanol, ethylene glycol and water, and a mixed solvent of ethanol and toluene is preferably used.
In the invention, after the reaction is finished, mixed liquor (volume ratio is 1: 1) of toluene and 5% sulfuric acid is added into the mixed system to be mixed, then the mixed system is stood for layering, the separated toluene layer is washed for 3 times, the solvent is distilled and removed under reduced pressure, and the obtained crude episulfide compound is purified by a silica gel column to obtain the pure poly-branched thioether type episulfide compound.
The multi-branched thioether-type ring sulfur compound synthesized by the invention has high purity and less impurity content, can inhibit the problems of color tone, turbidity and vein of the plastic lens obtained after curing, is suitable for synthesizing the plastic lens, is further used for various purposes such as cameras, projector lenses, prisms, optical fibers, optical filters, automobile optical lenses and the like, and has wide application prospect particularly on optical materials and elements such as plastic lenses, glass-plastic mixed optical lenses used in different occasions, camera lenses and the like.
The invention also provides a multi-branched thioether-type ring sulfur compound with a structure shown in a formula (4) prepared by the preparation method,
wherein R is C1-C10 linear alkyl, C1-C10 branched alkyl, substituted aryl or unsubstituted aryl,
m is an integer of 0 to 4,
n is an integer of 2 to 4.
According to the invention, R is preferably a linear alkyl group from C2 to C6, a branched alkyl group from C2 to C6, a substituted aryl group from C7 to C15 or an unsubstituted aryl group from C6 to C15, preferably CH3-、-CH2-、
R1CH2-、
Phenyl, methylphenyl, halophenyl, naphthyl, anthryl, phenanthryl or fluorenyl; wherein, R is1Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isopropyl, tert-butyl, n-pentyl, isopentyl, n-hexyl or phenyl.
More specifically, the multi-branched thioether-type ring sulfur compound with the structure of the formula (4) is represented by a formula (4-1) or a formula (4-2),
the invention also provides an optical material, which is obtained by mixing and curing the polymerizable composition;
wherein the polymerizable composition comprises: the multi-branched thioether-type cyclic sulfur compound, sulfur, polythiol and thioether described in the present invention.
According to the invention, the thioether is one or two of bis (beta-epithiopropyl) thioether and bis (beta-epithiopropyl) disulfide.
According to the present invention, the polythiol is not particularly limited, and examples thereof include methanedithiol, 1, 2-ethanedithiol, 1, 2, 3-propanetrithiol, 1, 2-cyclohexanedithiol, bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (mercaptopropylthio) methane, tetrakis (mercaptomethyl) methane, diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), and the like, Trimethylolethane tris (2-mercaptoacetate), trimethylolethane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1, 3-bis (mercaptomethyl) benzene, 1, 3, 3-tetrakis (mercaptomethylthio) propane, aliphatic polythiol compounds such as 1, 1, 2, 2-tetrakis (mercaptomethylthio) ethane, 2, 5-dimercaptomethyl-1, 4-dithiane, 2, 5-dimercapto-1, 4-dithiane, 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, 4, 8 or 4, 7 or 5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, and the like; and aromatic polythiol compounds such as 1, 2-dimercaptobenzene, 1, 3-dimercaptobenzene, 1, 4-dimercaptobenzene, 1, 2-bis (mercaptomethyl) benzene, 1, 3-bis (mercaptomethyl) benzene, 1, 4-bis (mercaptomethyl) benzene, 1, 2-bis (mercaptoethyl) benzene, 1, 3-bis (mercaptoethyl) benzene, 1, 4-bis (mercaptoethyl) benzene, 1, 3, 5-trimercaptobenzene, 1, 3, 5-tris (mercaptomethyl) benzene, 1, 3, 5-tris (mercaptomethyleneoxy) benzene, 1, 3, 5-tris (mercaptoethyloxy) benzene, 2, 5-methylbenzenethiol, 3, 4-methylbenzenethiol, and 1, 5-naphthalenedithiol; in the present invention, the polythiol is preferably bis (mercaptoethyl) sulfide, 1, 3-bis (mercaptomethyl) benzene, 1, 3, 3-tetrakis (mercaptomethylthio) propane, 1, 2, 2-tetrakis (mercaptomethylthio) ethane, 2, 5-dimercaptomethyl-1, 4-dithiane, pentaerythritol tetrakis (3-mercaptopropionate), 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, and 5, 7-dimercaptomethyl-1, 11-dimercapto-3, one or more of 6, 9-trithioundecane.
According to the invention, the sulfur in the optical material is preferably sulfur, the purity is more than 99.0%, and the particle size is less than 30 meshes; the grain diameter of the preferred purity of more than 99.9 percent is less than 60 meshes;
according to the present invention, the polymerizable composition further comprises one or more of a polymerization catalyst, an internal mold release agent, a light stabilizer, a bluing agent, an ultraviolet absorber, an antioxidant and a dye. Among them, as the polymerization catalyst in the polymerizable composition, amines, phosphines, esters, anhydrides, quaternary ammonium salts, quaternary phosphonium salts, lewis acids, organic acids and salts thereof, radical polymerization catalysts, cationic catalysts, and the like can be generally used. In the scheme, N-dimethylbenzylamine, N-dimethylcyclohexylamine or N, N-dicyclohexylmethylamine in the amine catalyst is preferably selected; the amount of the polymerization catalyst is 0.001 to 10 wt%, preferably 0.01 to 1 wt%, based on the total weight of the sulfur-containing compound; as the internal mold release agent in the polymerizable composition, commercially available acidic phosphoric acid esters can be used, and ZelecUN from STEPAN corporation; as the light stabilizer in the polymerizable composition, a hindered amine compound can be used, and in this case, Tinuvin123, Tinuvin144, Tinuvin292, Tinuvin765, Tinuvin770 DF; the ultraviolet absorber in the polymerizable composition can be any of a benzophenone ultraviolet absorber, a triazine ultraviolet absorber and a benzotriazole ultraviolet absorber which are commonly used, and can be used alone or in a mixture; by curing the polymerizable composition for optical materials in the present patent, a transparent material excellent in transparency, refractive index, heat resistance and strength can be obtained; tg of 60 ℃ or higher, preferably 70 ℃ or higher; a refractive index of 1.74 or more, preferably 1.76 or more;
the optical material provided by the invention can be used for various purposes such as camera lenses, projector lenses, prisms, optical lenses for automobiles and the like by curing the optical material obtained by the polymerizable composition and obtaining elements with different shapes by different molds, and is particularly suitable for manufacturing plastic elements in spectacle lenses and glass-plastic mixed optical lenses, wherein the optical material is a transparent material with excellent transparency, refractive index, heat resistance and strength, and the Tg is more than 60 ℃, preferably more than 70 ℃; the refractive index is 1.74 or more, preferably 1.76 or more.
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Synthesis of tetrakis (epithiopropylthiomethyl) methane
1. Synthesis of pentaerythritol tetrathiol:
firstly, placing 300mL of deionized water in a four-mouth bottle, heating to 60 ℃, adding 34g of pentaerythritol into hot water, stirring, adding 80g of thiourea and 102g of hydrochloric acid with the mass fraction of 37%, heating to more than 100 ℃, and carrying out reflux reaction for 5 hours to obtain isothiourea salt; then reducing the temperature of the system to 40 ℃, adding 85g of ammonia water solution with the mass fraction of 25% within 30min, adding 400mL of toluene solution, heating the system, carrying out alkaline hydrolysis reaction for 5h at 50 ℃, standing for layering after the completion, cutting a material layer, and respectively carrying out acid washing, water washing and water washing on the material layer at 55 ℃ according to the mass ratio of 1: 1, wherein the water washing uses degassed water with the oxygen concentration of 5 mg/L; after impurities are removed by water washing, 48g of purified pentaerythritol tetrathiol product is obtained by removing the solvent and water under the conditions of introducing nitrogen, the temperature of 75 ℃ and the pressure of less than-0.098 MPa, the yield is 96 percent, and the product chromaticity is 19;
2. synthesis of tetrakis (epoxypropylthiomethyl) methane:
taking 40g of pentaerythritol tetrathiol prepared by the reaction in the previous step, dropwise adding 120g of a sodium hydroxide solution with the mass fraction of 30%, controlling the temperature of the system to be not more than 10 ℃, keeping the temperature for 20min after the dropwise adding is finished, then beginning to dropwise add 80g of epoxy chloropropane into the system, controlling the dropwise adding speed to keep the temperature of the system at 15 ℃, keeping the temperature for 2h after the dropwise adding is finished, adding 500mL of toluene and 500mL of water after the reaction is finished, washing the toluene layer for three times by using degassed water, and distilling to remove the solvent to obtain 80g of tetra (epoxypropylthiomethyl) methane;
3. synthesis of tetrakis (epithiopropylthiomethyl) methane
To 80g of the resulting tetrakis (epoxypropylthiomethyl) methane, 300mL of toluene, 300mL of methanol, 88g of thiourea, and 1.5g of acetic acid were added, followed by stirring at 20 ℃ for 20 hours; and then adding 500mL of toluene and 500mL of 5% sulfuric acid solution, washing the toluene layer for 3 times, distilling to remove the solvent to obtain 60g of crude tetrakis (epithiopropylthiomethyl) methane, and further purifying the crude product with a silica gel column to obtain 40g of crude tetrakis (epithiopropylthiomethyl) methane product with the product chromaticity of 73.
Example 2
Synthesis of tetrakis (epithiopropylthiomethyl) methane
1. Synthesis of pentaerythritol tetrathiol:
firstly, putting 500mL of deionized water into a four-mouth bottle, heating to 60 ℃, adding 39g of pentaerythritol into hot water, stirring, adding 100g of thiourea and 115g of hydrochloric acid with the mass fraction of 37%, heating to more than 100 ℃, and carrying out reflux reaction for 5 hours to obtain isothiourea salt; then reducing the temperature of the system to 40 ℃, adding 87g of ammonia water solution with the mass fraction of 25% within 30min, adding 400mL of toluene solution, heating the system, carrying out alkaline hydrolysis reaction for 5h at 50 ℃, standing for layering after the completion, cutting a material layer, and respectively carrying out acid washing, water washing and water washing on the material layer at 55 ℃ according to the mass ratio of 1: 1, wherein the water washing uses degassed water with the oxygen concentration of 5 mg/L; after impurities are removed by water washing, 53g of purified pentaerythritol tetrathiol product is obtained by removing the solvent and water under the conditions of introducing nitrogen, the temperature of 75 ℃ and the pressure of less than-0.098 MPa, the yield is 92 percent, and the product chromaticity is 8;
2. synthesis of tetrakis (epoxypropylthiomethyl) methane:
taking 40g of pentaerythritol tetrathiol prepared by the reaction in the previous step, dropwise adding 110g of a 30% sodium hydroxide solution into the pentaerythritol tetrathiol, controlling the temperature of the system to be not more than 10 ℃, keeping the temperature for 20min after the dropwise adding is finished, then beginning to dropwise add 76g of epoxy chloropropane into the system, controlling the dropwise adding speed to keep the temperature of the system at 15 ℃, keeping the temperature for 2h after the dropwise adding is finished, adding 500mL of toluene and 500mL of water after the reaction is finished, washing the toluene layer for three times by using degassed water, and distilling to remove the solvent to obtain 77g of tetrakis (epoxypropylthiomethyl) methane;
3. synthesis of tetrakis (epithiopropylthiomethyl) methane
To 77g of tetrakis (epoxypropylthiomethyl) methane thus obtained were added 300mL of toluene, 300mL of methanol, 85g of thiourea and 1.2g of acetic acid, and the mixture was stirred at 20 ℃ for 20 hours; and then adding 500mL of toluene and 500mL of 5% sulfuric acid solution, washing the toluene layer for 3 times, distilling to remove the solvent to obtain 53g of crude tetrakis (epithiopropylthiomethyl) methane, and further purifying the crude product with a silica gel column to obtain 36g of the tetrakis (epithiopropylthiomethyl) methane product with the product chromaticity of 32.
Tetrakis (thiopropylthio methyl) methane used in the following experiments was synthesized in this way.
Example 3
Synthesis of tris (epithiopropylthiomethyl) ethane
1. Synthesis of trimercapto methyl ethane
Firstly, putting 200mL of deionized water into a four-mouth bottle, adding 30g of trimethylolethane into the deionized water at room temperature, stirring, then adding 60g of thiourea and 78g of hydrochloric acid with the mass fraction of 37%, heating to more than 100 ℃, and carrying out reflux reaction for 5 hours to obtain isothiourea salt; then reducing the temperature of the system to 40 ℃, adding 55g of ammonia water solution with the mass fraction of 25% within 30min, adding 200mL of toluene solution, heating the system, carrying out alkaline hydrolysis reaction for 5h at 50 ℃, standing for layering after the completion, cutting a material layer, and respectively carrying out acid washing, water washing and water washing on the material layer at 55 ℃ according to the mass ratio of 1: 1, wherein the water washing uses degassed water with the oxygen concentration of 5 mg/L; after impurities are removed by water washing, the solvent and water are removed under the conditions of introducing nitrogen, the temperature of 75 ℃ and the pressure of less than-0.098 MPa to obtain 40g of purified trimercapto methyl ethane, the reaction yield of the step is 96 percent, and the product chromaticity is 15;
2. synthesis of tris (epoxypropylthiomethyl) ethane
Taking 25g of trithiol methyl ethane prepared by the previous reaction, dropwise adding 60g of sodium hydroxide solution with the mass fraction of 30%, controlling the temperature of the system to be not more than 10 ℃, keeping the temperature for 20min after dropwise adding, then beginning to dropwise add 43g of epoxy chloropropane into the system, controlling the dropwise adding speed to keep the temperature of the system at 15 ℃, keeping the temperature for 2h after dropwise adding, adding 200mL of toluene and 200mL of water after reaction, washing the toluene layer for three times by using degassed water, and distilling to remove the solvent to obtain 48g of tri (epoxypropylthiomethyl) ethane;
3. synthesis of tris (epithiopropylthiomethyl) ethane
To 48g of the obtained tris (epoxypropylthiomethyl) ethane were added 300mL of toluene, 300mL of methanol, 40g of thiourea, and 0.8g of acetic acid, and the mixture was stirred at 20 ℃ for 20 hours; and then 200mL of toluene and 200mL of 5 mass percent sulfuric acid solution are added, the toluene layer is washed with water for 3 times, the solvent is removed by distillation, 37g of a crude product of the tri (thiopropylthiomethyl) ethane is obtained, the crude product is further purified by a silica gel column, and finally 24g of a tri (thiopropylthiomethyl) ethane product is obtained, wherein the product chromaticity is 51.
The tris (epithiopropylthiomethyl) ethane used in the following process was synthesized by this method.
Example 4
Synthesis of tris (epithiopropylthiomethyl) ethane
1. Synthesis of trimercapto methyl ethane
Firstly, placing 400mL of deionized water in a four-mouth bottle, adding 30g of trimethylolethane at room temperature, stirring, adding 60g of thiourea and 78g of hydrochloric acid with the mass fraction of 37%, heating to more than 100 ℃, and carrying out reflux reaction for 5 hours to obtain isothiourea salt; then reducing the temperature of the system to 40 ℃, adding 55g of ammonia water solution with the mass fraction of 25% within 30min, adding 200mL of toluene solution, heating the system, carrying out alkaline hydrolysis reaction for 5h at 50 ℃, standing for layering after the completion, cutting a material layer, and respectively carrying out acid washing, water washing and water washing on the material layer at 55 ℃ according to the mass ratio of 1: 1, wherein the water washing uses degassed water with the oxygen concentration of 5 mg/L; after impurities are removed by water washing, the solvent and water are removed under the conditions of introducing nitrogen, the temperature of 75 ℃ and the pressure of less than-0.098 MPa to obtain 40g of purified trimercapto methyl ethane, the reaction yield of the step is 96 percent, and the product chroma is 7;
2. synthesis of tris (epoxypropylthiomethyl) ethane
Taking 25g of trithiol methyl ethane prepared by the reaction in the previous step, dropwise adding 60g of sodium hydroxide solution with the mass fraction of 30%, controlling the temperature of the system to be not more than 10 ℃, keeping the temperature for 20min after dropwise adding, then beginning to dropwise add 43g of epoxy chloropropane into the system, controlling the dropwise adding speed to keep the temperature of the system at 15 ℃, keeping the temperature for 2h after dropwise adding, adding 200mL of toluene and 200mL of water after the reaction is finished, washing the toluene layer three times by using degassed water, and distilling to remove the solvent, wherein 48g of tri (epoxypropylthiomethyl) ethane;
3. synthesis of tris (epithiopropylthiomethyl) ethane
To 48g of the obtained tris (epoxypropylthiomethyl) ethane were added 300mL of toluene, 300mL of methanol, 40g of thiourea, and 0.8g of acetic acid, and the mixture was stirred at 20 ℃ for 20 hours; and then 200mL of toluene and 200mL of 5 mass percent sulfuric acid solution are added, the toluene layer is washed with water for 3 times, the solvent is removed by distillation, 37g of a crude product of the tri (thiopropylthiomethyl) ethane is obtained, the crude product is further purified by a silica gel column, and finally 24g of a tri (thiopropylthiomethyl) ethane product is obtained, wherein the product chromaticity is 28.
Example 5
Mixing tetra (epithiopropylthiomethyl) methane, bis (mercaptoethyl) thiol, sulfur, tetra-n-butylammonium bromide and di-n-butyltin dichloride prepared in example 2 in a mass ratio of 80: 19: 1: 0.02: 0.05, and performing vacuum degassing while mixing to obtain a polymerizable composition for an optical material, heating the polymerizable composition at 30 ℃ for 10 hours, then heating to 100 ℃ for 12 hours, heating at 100 ℃ for 6 hours, naturally cooling, and annealing at 120 ℃ for 1 hour to obtain an optical material with a refractive index of 1.715, which is detailed in table 1;
example 6
Mixing tetra (episulfide propylthiomethyl) methane, 1, 3-bis (mercapto methyl) benzene, sulfur, tetra-n-butylammonium bromide and di-n-butyltin dichloride prepared in example 2 according to a mass ratio of 78: 8: 14: 0.01: 0.03, and performing vacuum degassing while mixing to obtain a polymerizable composition for an optical material, heating the polymerizable composition at 30 ℃ for 10 hours, then heating to 100 ℃ for 12 hours, heating at 100 ℃ for 6 hours, naturally cooling, and then annealing at 120 ℃ for 1 hour, wherein the refractive index of the obtained optical material is 1.741, and the details are shown in table 1;
example 7
Mixing tetra (cyclopropylthiomethyl) methane, bis (mercaptoethyl) thiol, sulfur, tetra-n-butylammonium bromide and di-n-butyltin dichloride prepared in example 2 in a mass ratio of 70: 6: 24: 0.02: 0.05, and vacuum degassing while mixing to obtain a polymerizable composition for an optical material, heating the polymerizable composition at 30 ℃ for 10 hours, then heating the polymerizable composition to 100 ℃ for 12 hours, heating the polymerizable composition at 100 ℃ for 6 hours, naturally cooling the polymerizable composition, and annealing the polymerizable composition at 120 ℃ for 1 hour to obtain an optical material with a refractive index of 1.765, which is detailed in table 1;
example 8
Mixing tetra (episulfide propylthiomethyl) methane, 1, 3-bis (mercapto methyl) benzene, sulfur, tetra-n-butylammonium bromide and di-n-butyltin dichloride prepared in example 2 according to a mass ratio of 80: 10: 0.02: 0.04, and performing vacuum degassing while mixing to obtain a polymerizable composition for an optical material, heating the polymerizable composition at 30 ℃ for 10 hours, then heating the polymerizable composition to 100 ℃ for 12 hours, heating the polymerizable composition at 100 ℃ for 6 hours, naturally cooling the polymerizable composition, and annealing the mixture at 120 ℃ for 1 hour to obtain the optical material with a refractive index of 1.730, which is detailed in table 1;
example 9
Mixing tris (cyclopropylthiomethyl) ethane, 1, 3-bis (mercaptomethyl) benzene, sulfur, tetra-n-butylammonium bromide and di-n-butyltin dichloride prepared in example 4 in a mass ratio of 78: 10: 12: 0.02: 0.04, and vacuum degassing while mixing to obtain a polymerizable composition for an optical material, heating the polymerizable composition at 30 ℃ for 10 hours, then heating the polymerizable composition to 100 ℃ for 12 hours, heating the polymerizable composition at 100 ℃ for 6 hours, naturally cooling the polymerizable composition, and annealing the polymerizable composition at 120 ℃ for 1 hour to obtain an optical material with a refractive index of 1.716, which is detailed in table 1;
example 10
Tris (cyclopropylthiomethyl) ethane, bis (mercaptoethyl) thiol, sulfur, tetra-n-butylammonium bromide and di-n-butyltin dichloride prepared in example 4 were mixed in a mass ratio of 70: 10: 20: 0.02: 0.04, and vacuum degassing was performed while mixing to obtain a polymerizable composition for an optical material, and then the polymerizable composition was heated at 30 ℃ for 10 hours, then heated to 100 ℃ over 12 hours, heated at 100 ℃ for 6 hours, naturally cooled, and annealed at 120 ℃ for 1 hour to obtain an optical material having a refractive index of 1.740, as detailed in table 1;
TABLE 1
In conclusion, the episulfide compound monomer obtained by the method for preparing the multi-branched thioether-type episulfide compound for the optical material provided by the invention has high quality and low impurity content, and can inhibit the problems of color tone, turbidity and vein of the plastic lens obtained after curing. Furthermore, the optical material obtained by curing the episulfide compound serving as the raw material of the polymerizable composition has the refractive index of more than 1.75 and the glass transition temperature of more than 68 ℃, is suitable for synthesizing plastic lenses, is further used for various purposes such as cameras, projector lenses, prisms, optical fibers, optical filters, automobile optical lenses and the like, and particularly has wide application prospect on optical materials and elements such as plastic lenses, glass-plastic mixed optical lenses used in different occasions, camera lenses and the like.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (2)
1. A method for preparing a multi-branched thioether-type ring sulfur compound, comprising:
1) reacting a compound shown in a formula (1) with thiourea under an acidic condition to generate isothiourea salt;
wherein R is a C1-C10 linear alkyl group and a C1-C10 branched alkyl group, m is an integer of 0-4, and n is an integer of 2-4;
2) hydrolyzing isothiourea salt under alkaline conditions to obtain a compound shown as a formula (2);
3) reacting the compound shown in the formula (2) with epoxy chloropropane to obtain a compound shown in a formula (3);
4) converting the compound of formula (3) into a compound of formula (4);
2. the method according to claim 1, wherein the solvent for the reaction of step 1) is water;
the mass ratio of the sum of the mass of the compound represented by the formula (1) and thiourea to the water is 1: (3.0-8.0).
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