Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D301/00—Preparation of oxiranes
  • C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
  • C07D303/02—Compounds containing oxirane rings
  • C07D303/34—Compounds containing oxirane rings with hydrocarbon radicals, substituted by sulphur, selenium or tellurium atoms

Definitions

• the present invention relates to a sulfur-containing epoxy compound and a method for producing the same.
• the present invention relates to a sulfur-containing epoxy compound used as a raw material for an optical material such as a plastic lens, a prism, an optical fiber, an information recording substrate, and a filter, particularly an episulfide compound suitably used for a plastic lens, and a production method thereof.
• This episulfide compound is obtained by producing a sulfur-containing epoxy compound in which the sulfur atom of the epithio moiety is an oxygen atom, and then thialating.
• the production methods shown in Patent Documents 1 to 3 have been proposed, and the yield is improved and the transparency of the resin obtained by curing the episulfide compound obtained by thialation is improved. ing.
• these production methods use hydrogen sulfide as a main raw material and are difficult to handle.
• a method for producing without using hydrogen sulfide is disclosed in Patent Document 1, but the yield is low and a large amount of oligomers are produced, and subsequent distillation purification is difficult. Accordingly, it has been desired to develop a method for producing a sulfur-containing epoxy compound that does not use hydrogen sulfide and suppresses the formation of oligomers.
• an episulfide compound having a disulfide as disclosed in Patent Document 4 has also been proposed.
• This episulfide compound is obtained by producing a sulfur-containing epoxy compound in which the sulfur atom of the epithio moiety is an oxygen atom, and then thialating.
• this production method uses hydrogen sulfide as a main raw material and is sometimes difficult to handle.
• disulfide is the limit in the method shown in Patent Document 4, and it is impossible to produce an epoxy compound having a polysulfide of tri or higher.
• a method was desired. Accordingly, development of a method for producing an epoxy compound having polysulfide without using hydrogen sulfide has been desired.
• the problem to be solved by the present invention is to provide a method for producing a bis ( ⁇ -epoxypropyl) sulfide of a sulfur-containing epoxy compound in a high yield without using hydrogen sulfide and suppressing the formation of oligomers.
• Another problem to be solved by the present invention is that bis ( ⁇ -epoxypropyl) sulfide, a sulfur-containing epoxy compound, is produced in a single step with good yield without using hydrogen sulfide and suppressing oligomer formation. It is to provide a way to do.
• another problem to be solved by the present invention is to provide a method for producing a bis ( ⁇ -epoxypropyl) polysulfide of an epoxy compound having a polysulfide without using hydrogen sulfide.
• the epoxy compound which has a polysulfide was obtained without using hydrogen sulfide by the manufacturing method which makes an epihalohydrin and a polysulfide metal react, and obtains a sulfur-containing epoxy compound. That is, the present invention is as follows. ⁇ 1> A metal compound selected from the group consisting of metal hydrosulfide, metal sulfide and polysulfide metal is added to epihalohydrin so that the molar ratio of epihalohydrin / metal compound is 5 to 20 at -5 to 30 ° C. A process for producing bis ( ⁇ -epoxypropyl) sulfide or bis ( ⁇ -epoxypropyl) polysulfide.
• ⁇ 2> The method according to ⁇ 1>, wherein the epihalohydrin is epichlorohydrin, and the metal hydrosulfide is sodium hydrosulfide or potassium hydrosulfide.
• the epihalohydrin is epichlorohydrin, and the metal sulfide is sodium sulfide or potassium sulfide.
• the epihalohydrin is epichlorohydrin, and the metal polysulfide is sodium polysulfide or potassium polysulfide.
• ⁇ 5> After adding metal hydrosulfide to epihalohydrin at ⁇ 5 to 30 ° C.
• the basic compound is further added to the basic compound / the water.
• the production method of the present invention makes it possible to produce bis ( ⁇ -epoxypropyl) sulfide, which is a sulfur-containing epoxy compound that suppresses the formation of oligomers without using hydrogen sulfide, which was not obtained by the conventional production method. It was. Since hydrogen sulfide is not used and oligomer formation is suppressed, bis ( ⁇ -epoxypropyl) sulfide, a sulfur-containing epoxy compound, can be easily obtained in a high yield, which is very significant.
• the production method of the present invention eliminates the formation of oligomers without using hydrogen sulfide, which was not obtained by the production method of the prior art, and suppresses the formation of oligomers in a single step with a high yield of bis ( ⁇ -epoxy) Propyl sulfide can be produced. Since hydrogen sulfide is not used and the formation of oligomers is suppressed in one step, the sulfur-containing epoxy compound bis ( ⁇ -epoxypropyl) sulfide is easily obtained in a high yield, which is very significant. Furthermore, the production method of the present invention makes it possible to produce an epoxy compound having polysulfide without using hydrogen sulfide, which was not obtained by the production method of the prior art.
• a metal compound selected from the group consisting of metal hydrosulfide, metal sulfide and polysulfide metal is added to epihalohydrin so that the molar ratio of epihalohydrin / metal compound is 5 to 20 at ⁇ 5 to 30 ° C.
• a reaction process for producing bis ( ⁇ -epoxypropyl) sulfide or bis ( ⁇ -epoxypropyl) polysulfide is produced.
• the oligomer which the 1st preferable embodiment of this invention tends to suppress a by-product is a compound obtained by a reaction intermediate body multimerizing, and a typical structure is a structure shown by following (2) Formula.
• (2) Quantifying the compound having the formula structure is an indicator of whether or not the formation of the oligomer that is the target of the present invention can be suppressed.
• the epihalohydrin used in the first preferred embodiment of the present invention includes all compounds, but is preferably an easily available epichlorohydrin.
• the metal hydrosulfide used in the first preferred embodiment of the present invention includes all compounds, but is preferably sodium hydrosulfide and potassium hydrosulfide which are easily available, and more preferably sodium hydrosulfide.
• the reaction of epihalohydrin and metal hydrosulfide which is the first-stage reaction of the first preferred embodiment of the present invention, is as follows. Reaction is performed by adding metal hydrosulfide to epihalohydrin. At this time, the metal hydrosulfide is added so that the molar ratio of epihalohydrin / metal hydrosulfide is 5-20. Preferably, it is 5 to 15, more preferably 5 to 10.
• the molar ratio does not represent the actual molar ratio in the reaction system, but represents the molar ratio between the amount of epihalohydrin charged and the final amount of metal hydrosulfide added.
• the epihalohydrin / metal hydrosulfide molar ratio is less than 5, a large amount of the compound of the formula (2) is produced, resulting in a decrease in yield. Furthermore, in the case of subsequent distillation purification, the compound of the formula (2) remains difficult to treat because it remains as a residue.
• the molar ratio of epihalohydrin / metal hydrosulfide exceeds 20, epihalohydrin is used in a large excess, which is not economically preferable.
• the addition of the metal hydrosulfide to the epihalohydrin is preferably not the method of adding it at once but the method of gradually adding it in order to reduce the formation of the compound of formula (2).
• the solvent is not particularly required as long as epihalohydrin and metal hydrosulfide react with each other, but a solvent is preferably used.
• a solvent it is preferably water, alcohols, ethers, aliphatic hydrocarbons, aromatic hydrocarbons or halogenated hydrocarbons, more preferably water or alcohols, still more preferably. Water and methanol, most preferably methanol. These solvents may be used alone or in combination.
• the solvent is preferably used for dissolving the metal hydrosulfide. If it says further, it is preferable to make epihalohydrin and the metal hydrosulfide dissolved in the solvent react, More preferably, it is dropping the metal hydrosulfide dissolved in the solvent into the epihalohydrin.
• the reaction temperature is ⁇ 5 to 30 ° C., preferably 0 ° C. to 20 ° C., and most preferably 5 to 15 ° C. When the temperature is lower than ⁇ 5 ° C., the reaction rate is lowered, which is not economically preferable.
• the basic compound used in the first preferred embodiment of the present invention is not particularly limited, and any basic compound may be used, but is preferably an amine, an alkali metal or an alkaline earth metal salt, more preferably. Is an alkali metal or alkaline earth metal salt.
• Preferred examples thereof are sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide. Of these, sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide are preferable, and sodium hydroxide and potassium hydroxide are more preferable.
• the basic compound is added so that the molar ratio of basic compound / metal hydrosulfide is 1.0 to 3.5. More preferably, it is 1.2 to 3.0, and still more preferably 1.5 to 3.0.
• the molar ratio does not represent the molar ratio in the actual reaction system, but represents the molar ratio between the addition amount of the basic compound and the addition amount of the metal hydrosulfide in the first stage reaction.
• the basic compound is less than 1.0 in the basic compound / metal hydrosulfide molar ratio, the epoxy compound is not sufficiently formed, and the yield decreases.
• the basic compound exceeds 3.5 in the basic compound / metal hydrosulfide molar ratio, the water washing operation for removing the excess base is increased, which is economically undesirable.
• the addition of the basic compound to the reaction product obtained in the first stage reaction is preferably not a single addition but a gradual addition in terms of controlling the reaction.
• the solvent is not particularly required as long as the basic compound, the reaction product of epihalohydrin and metal hydrosulfide are reacted, but a solvent is preferably used.
• a solvent it is preferably water, alcohols, ethers, aliphatic hydrocarbons, aromatic hydrocarbons or halogenated hydrocarbons, more preferably water or alcohols, still more preferably. Water and methanol, most preferably water. These may be used alone or in combination.
• the solvent is preferably used for dissolving the basic compound. Furthermore, if it says, it is preferable to make it react with the reaction product of an epihalohydrin and a metal hydrosulfide after melt
• dissolving a basic compound in a solvent More preferably, after dissolving a basic compound in a solvent, epihalohydrin and hydrosulfide. It is dripping to the reaction product with a metal.
• the reaction temperature in the second stage is ⁇ 5 to 30 ° C., preferably 0 ° C. to 20 ° C., and most preferably 5 to 15 ° C. When the temperature is lower than ⁇ 5 ° C., the reaction rate is lowered, which is not economically preferable.
• an organic solvent and extract the bis ( ⁇ -epoxypropyl) sulfide of the target sulfur-containing epoxy compound.
• Preferred are hydrocarbons, ethers, aliphatic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons, and more preferred are aromatic hydrocarbons and halogenated hydrocarbons.
• Preferable specific examples are toluene, benzene, xylene, dichloromethane and chloroform, most preferably toluene.
• the desired sulfur-containing epoxy compound bis ( ⁇ -epoxypropyl) sulfide is obtained.
• the sulfur-containing epoxy compound represented by the formula (1) is suppressed without using hydrogen sulfide, which was not obtained by the production method of the prior art, and suppresses the formation of oligomers. Manufacture is possible. Since hydrogen sulfide is not used and the production of the compound represented by the formula (2) is suppressed, a bis ( ⁇ -epoxypropyl) sulfide, which is a sulfur-containing epoxy compound, can be easily obtained in a high yield.
• a second preferred embodiment of the present invention is characterized in that a metal sulfide is added to epihalohydrin at ⁇ 5 to 30 ° C. so that the molar ratio of epihalohydrin / metal sulfide is 5 to 20 and reacted.
• 1) It relates to a process for producing a sulfur-containing epoxy compound (bis ( ⁇ -epoxypropyl) sulfide) represented by the formula:
• the oligomer which the 2nd preferable embodiment of this invention tends to suppress a by-product is a compound obtained by multimerizing a reaction intermediate, and a typical structure is a structure shown by following (2) Formula.
• the epihalohydrin used in the second preferred embodiment of the present invention encompasses all compounds, but is preferably readily available epichlorohydrin.
• the metal sulfide used in the second preferred embodiment of the present invention includes all compounds, but is preferably sodium sulfide or potassium sulfide which is easily available, and more preferably sodium sulfide.
• the reaction between epihalohydrin and metal sulfide is as follows.
• a metal sulfide is added to epihalohydrin and reacted.
• it is added so that the molar ratio of epihalohydrin / metal sulfide is 5-20.
• the molar ratio does not represent the actual molar ratio in the reaction system, but represents the molar ratio between the charged amount of epihalohydrin and the final added amount of metal sulfide.
• the epihalohydrin / metal sulfide molar ratio is less than 5, a large amount of the compound of the formula (2) is produced, resulting in a decrease in yield.
• the compound of the formula (2) remains difficult to treat because it remains as a residue.
• the molar ratio of epihalohydrin / metal sulfide exceeds 20, it is not economically preferable because epihalohydrin is used in a large excess.
• the addition of the metal sulfide to the epihalohydrin is preferably a method in which the metal sulfide is added gradually rather than all at once because the formation of the compound of the formula (2) is small.
• the solvent is not particularly required as long as epihalohydrin and metal sulfide react with each other, but a solvent is preferably used.
• a solvent it is preferably water, alcohols, ethers, aliphatic hydrocarbons, aromatic hydrocarbons or halogenated hydrocarbons, more preferably water or alcohols, still more preferably. Water and methanol, most preferably water. These solvents may be used alone or in combination.
• the solvent is preferably used for dissolving the metal sulfide. Further, it is preferable to react the epihalohydrin and the metal sulfide dissolved in the solvent, more preferably dropping the metal sulfide dissolved in the solvent into the epihalohydrin.
• the reaction temperature is ⁇ 5 to 30 ° C., preferably 0 ° C. to 20 ° C., and most preferably 5 to 15 ° C. When the temperature is lower than ⁇ 5 ° C., the reaction rate is lowered, which is not economically preferable.
• a basic compound may be further reacted in order to complete the reaction.
• the basic compound is not particularly limited, and any basic compound may be used, but is preferably an amine, an alkali metal or an alkaline earth metal salt, and more preferably an alkali metal or an alkaline earth metal salt.
• Preferred examples thereof are sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide. Of these, sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide are preferable, and sodium hydroxide and potassium hydroxide are more preferable.
• the basic compound is 1 equivalent or less, more preferably 0.5 equivalent or less with respect to the metal sulfide.
• the solvent used in this case is not particularly limited, but is preferably water, alcohols, ethers, aliphatic hydrocarbons, aromatic hydrocarbons or halogenated hydrocarbons, more preferably water, alcohols. More preferred are water and methanol, and most preferred is water. These may be used alone or in combination.
• the basic compound is dissolved in a solvent and then added dropwise to the reaction product of epihalohydrin and metal sulfide.
• the reaction temperature is ⁇ 5 to 30 ° C., preferably 0 ° C.
• the reaction rate is lowered, which is not economically preferable. It is preferable to stir for 1 minute to 10 hours after completion of the dropping. More preferably, it is 5 minutes to 5 hours, and still more preferably 10 minutes to 3 hours.
• an organic solvent and extract the bis ( ⁇ -epoxypropyl) sulfide of the target sulfur-containing epoxy compound.
• Preferred are hydrocarbons, ethers, aliphatic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons, and more preferred are aromatic hydrocarbons and halogenated hydrocarbons.
• Preferable specific examples are toluene, benzene, xylene, dichloromethane and chloroform, most preferably toluene.
• the desired sulfur-containing epoxy compound bis ( ⁇ -epoxypropyl) sulfide is obtained.
• the production method of the second preferred embodiment of the present invention suppresses the formation of oligomers without using hydrogen sulfide, which was not obtained by the production method of the prior art, and improves the yield of the sulfur-containing epoxy compound in a single step with good yield. It became possible to manufacture. Since hydrogen sulfide is not used and the formation of oligomers is suppressed in one step, the sulfur-containing epoxy compound bis ( ⁇ -epoxypropyl) sulfide can be easily obtained in high yield.
• a third preferred embodiment of the present invention is a process for producing a sulfur-containing epoxy compound (bis ( ⁇ -epoxypropyl) polysulfide) represented by the following formula (3), characterized by reacting an epihalohydrin and a metal polysulfide.
• n represents an integer of 2 or more
• n is an integer from 2 to 5, most preferably n is 2.
• the epihalohydrin used in the third preferred embodiment of the present invention includes all compounds, but is preferably an easily available epichlorohydrin.
• the reaction between epihalohydrin and metal polysulfide is as follows.
• the metal polysulfide is preferably added to the epihalohydrin and reacted.
• the molar ratio of epihalohydrin / metal polysulfide is less than 5, the yield is reduced.
• the molar ratio of epihalohydrin / metal polysulfide exceeds 20, it is not economically preferable because epihalohydrin is used in a large excess.
• the solvent is not particularly required as long as epihalohydrin and metal polysulfide react with each other, but a solvent is preferably used.
• a solvent it is preferably water, alcohols, ethers, aliphatic hydrocarbons, aromatic hydrocarbons or halogenated hydrocarbons, more preferably water or alcohols, still more preferably. Water and methanol, most preferably water. These solvents may be used alone or in combination.
• the solvent is preferably used for dissolving the metal polysulfide. Furthermore, it is preferable to react the epihalohydrin and the metal polysulfide dissolved in the solvent, more preferably dropping the metal polysulfide dissolved in the solvent into the epihalohydrin.
• the reaction temperature is preferably ⁇ 5 to 30 ° C., more preferably 0 ° C. to 20 ° C., and most preferably 5 to 15 ° C.
• the temperature is lower than ⁇ 5 ° C., the reaction rate is decreased, which is not economically preferable.
• the temperature is higher than 30 ° C., the yield is decreased.
• it is preferable to stir for 1 minute to 10 hours after the addition of the metal polysulfide. More preferably, it is 5 minutes to 5 hours, and still more preferably 10 minutes to 3 hours.
• a basic compound may be further reacted to complete the reaction.
• the basic compound is not particularly limited, and any basic compound may be used, but is preferably an amine, an alkali metal or an alkaline earth metal salt, and more preferably an alkali metal or an alkaline earth metal salt.
• Preferred examples thereof are sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide. Of these, sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide are preferable, and sodium hydroxide and potassium hydroxide are more preferable.
• the basic compound is 1 equivalent or less, more preferably 0.5 equivalent or less with respect to the metal polysulfide.
• the solvent used in this case is not particularly limited, but is preferably water, alcohols, ethers, aliphatic hydrocarbons, aromatic hydrocarbons or halogenated hydrocarbons, more preferably water, alcohols. More preferred are water and methanol, and most preferred is water. These may be used alone or in combination.
• the basic compound is dissolved in a solvent and then added dropwise to the reaction product of epihalohydrin and metal polysulfide.
• the reaction temperature is ⁇ 5 to 30 ° C., preferably 0 ° C. to 20 ° C., and most preferably 5 to 15 ° C.
• the temperature is lower than ⁇ 5 ° C., the reaction rate is decreased, which is not economically preferable.
• the temperature is higher than 30 ° C., the yield is decreased. It is preferable to stir for 1 minute to 10 hours after completion of the dropping. More preferably, it is 5 minutes to 5 hours, and still more preferably 10 minutes to 3 hours.
• an organic solvent to extract the bis ( ⁇ -epoxypropyl) polysulfide of the target sulfur-containing epoxy compound.
• organic solvent Preferred are hydrocarbons, ethers, aliphatic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons, and more preferred are aromatic hydrocarbons and halogenated hydrocarbons.
• Preferable specific examples are toluene, benzene, xylene, dichloromethane and chloroform, most preferably toluene.
• the target sulfur-containing epoxy compound is obtained by distilling off the solvent from the organic layer thus obtained.
• Example 1 A solution prepared by dissolving 40 g (0.5 mol) of 70% sodium hydrosulfide in 100 ml of methanol in 232 g (2.5 mol) of epichlorohydrin (hereinafter abbreviated as EPCH) was added dropwise with stirring at 5 to 10 ° C., and then stirred for 1 hour. . Next, a solution obtained by dissolving 70 g (1.75 mol) of sodium hydroxide in 200 ml of water was added dropwise with stirring at 5 to 10 ° C., and then stirred for 1 hour.
• EPCH epichlorohydrin
• Example 2 In Example 1, Example 1 was repeated except that the amount of EPCH was changed to 925 g (10 mol). The results are shown in Table 1.
• Example 3 In Example 1, Example 1 was repeated except that the amount of sodium hydroxide was 20 g (0.5 mol). The results are shown in Table 1.
• Example 4 In Example 1, Example 1 was repeated except that the amount of EPCH was 925 g (10 mol) and the amount of sodium hydroxide was 20 g (0.5 mol). The results are shown in Table 1.
• Example 5 In Example 1, Example 1 was repeated except that the amount of EPCH was 463 g (5 mol) and the amount of sodium hydroxide was 40 g (1.0 mol). The results are shown in Table 1.
• Example 1 (Comparative Example 1) In Example 1, Example 1 was repeated except that the amount of EPCH was changed to 185 g (2 mol). Since the amount of EPCH was small, the yield decreased, and the compound of formula (2), which was an impurity, further increased. The results are shown in Table 1.
• Example 2 (Comparative Example 2) In Example 1, Example 1 was repeated except that the temperature from the start of dropping sodium hydrosulfide to the start of dropping sodium hydroxide was 35 ° C. Since the reaction temperature was high, the yield decreased and the compound of formula (2), which was an impurity, increased. The results are shown in Table 1.
• Example 3 (Comparative Example 3) In Example 1, Example 1 was repeated except that the temperature from the start of dropping sodium hydrosulfide to the start of dropping sodium hydroxide was -10 ° C. The yield decreased because the reaction temperature was low. The results are shown in Table 1.
• Example 6 250 ml of methanol was mixed and stirred at 232 g (2.5 mol) of epichlorohydrin (hereinafter abbreviated as EPCH) to 10 ° C. A solution obtained by dissolving 120 g (0.5 mol) of sodium sulfide nonahydrate in 1000 ml of water was added dropwise with stirring at 5 to 10 ° C., and then stirred for 1 hour. After completion of the reaction, the reaction mixture was extracted with 1000 ml of toluene, then washed with 500 ml of water until the pH of the washing water became 9 or less, and the solvent was distilled off to obtain 60 g of bis ( ⁇ -epoxypropyl) sulfide (yield 82%). The obtained bis ( ⁇ -epoxypropyl) sulfide was analyzed by liquid chromatography. As a result, the compound of the formula (2) was 4.8%. The results are shown in Table 2.
• Example 7 In Example 6, Example 6 was repeated except that the amount of EPCH was changed to 925 g (10 mol). The results are shown in Table 2.
• Example 8 In Example 6, Example 6 was repeated except that the amount of EPCH was changed to 463 g (5 mol). The results are shown in Table 2.
• Example 6 (Comparative Example 4) In Example 6, Example 6 was repeated except that the amount of EPCH was 185 g (2 mol). Since the amount of EPCH was small, the yield decreased, and the compound of formula (2), which was an impurity, further increased. The results are shown in Table 2.
• Example 6 (Comparative Example 5) In Example 6, Example 6 was repeated except that the reaction temperature was 35 ° C. Since the reaction temperature was high, the yield decreased and the compound of formula (2), which was an impurity, increased. The results are shown in Table 2.
• Example 6 (Comparative Example 6) In Example 6, Example 6 was repeated except that the reaction temperature was ⁇ 10 ° C. The yield decreased because the reaction temperature was low. The results are shown in Table 2.
• Example 9 232 g (2.5 mol) of epichlorohydrin was mixed with 250 ml of methanol and stirred at 10 ° C. A solution obtained by dissolving 28 g (0.25 mol) of sodium disulfide in 70 ml of water was added dropwise with stirring at 5 to 10 ° C., and then stirred for 2 hours. After completion of the reaction, the reaction mixture was extracted with 1000 ml of toluene, then washed with 500 ml of water until the pH of the washing water became 9 or less, and the solvent was distilled off to obtain 36 g (yield 80%) of bis ( ⁇ -epoxypropyl) disulfide. The results are shown in Table 3.
• Example 10 (Example 10) In Example 9, Example 9 was repeated except that the amount of EPCH was changed to 925 g (10 mol). The results are shown in Table 3.
• Example 11 In Example 9, Example 9 was repeated except that 0.25 mol of sodium trisulfide was used instead of sodium disulfide to obtain bis ( ⁇ -epoxypropyl) trisulfide in a yield of 62%. The results are shown in Table 3.
• Example 12 In Example 11, Example 11 was repeated except that the amount of EPCH was 925 g (10 mol). The results are shown in Table 3.
• Example 13 Example 9 was repeated except that 0.25 mol of sodium tetrasulfide was used instead of sodium disulfide to obtain bis ( ⁇ -epoxypropyl) tetrasulfide in a yield of 51%.
• the results are shown in Table 3.
• Example 15 Example 9 was repeated except that 0.25 mol of sodium pentasulfide was used instead of sodium disulfide to obtain bis ( ⁇ -epoxypropyl) pentasulfide in a yield of 35%.
• the results are shown in Table 3.
• Example 16 In Example 15, Example 15 was repeated except that the amount of EPCH was changed to 925 g (10 mol). The results are shown in Table 3.
• Example 9 (Comparative Example 7) In Example 9, Example 9 was repeated except that the amount of EPCH was 185 g (2 mol). The yield decreased because the amount of EPCH was small. The results are shown in Table 3.
• Example 9 (Comparative Example 8) In Example 9, Example 9 was repeated except that the reaction temperature was 35 ° C. The yield decreased because the reaction temperature was high. The results are shown in Table 3.
• Example 9 (Comparative Example 9) In Example 9, Example 9 was repeated except that the reaction temperature was ⁇ 10 ° C. The yield decreased because the reaction temperature was low. The results are shown in Table 3.

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