Method for producing purified epoxy compound

A method for producing tris(2,3-epoxypropyl) isocyanurate or tris(2-methyl-2,3-epoxypropyl) isocyanurate as a purified product which has an epoxide equivalent of 1.0 to 1.1 times the theoretical epoxide equivalent of the isocyanurate and forms a transparent liquid when molten, comprising steps (A) to (D):

• (A) reacting an epihalohydrin or a 2-methyl-epihalohydrin with isocyanuric acid in a reaction mixture containing isocyanuric acid and the epihalohydrin or the 2-methyl-epihalohydrin in a ratio of 1 mol of active hydrogen atoms of the isocyanuric acid to 1.2 to 60 mol of the epihalohydrin or the 2-methyl-epihalohydrin, and a catalytic amount of a tertiary amine, a quaternary ammonium base or salt, a tri-substituted phosphine or a quaternary phosphonium salt, thereby forming a reaction product containing a tris(2-hydroxy-3-halopropyl) isocyanurate or a tris(2-hydroxy-2-methyl-3-halopropyl) isocyanurate,
• (B) adding gradually to the reaction product in a vessel an alkali metal hydroxide as an aqueous solution having a concentration of 20 to 70 wt % of the hydroxide in a ratio of 1 to 2 mol of the hydroxide to 1 mol of active hydrogen atoms of the isocyanuric acid in the reaction product before the reaction in step (A) to cause and complete dehydrohalogenation to the isocyanurate in the reaction product and to form a slurry containing a precipitated alkali metal halide, while maintaining the slurry under agitation which causes the slurry to produce a stream circulating and ascending from the bottom along the inner side wall of the vessel to the surface of the slurry, turning there the ascending stream to a stream swirling downward and shearing across the swirling stream, thereby maintaining the slurry uniform, and removing by evaporation from the slurry the water added and caused by the reaction in a vacuum at a temperature of 10.degree. to 80.degree. C., thereby forming a final slurry containing tris(2,3-epoxypropyl) isocyanurate or tris(2-methyl-2,3-epoxypropyl) isocyanurate and an alkali metal halide generated by the reaction,
• (C) washing with water the final slurry in step (B) or a liquid product obtained by removing the alkali metal halide from the final slurry in step (B), thereby forming a refined liquid containing the isocyanurate, and
• (D) removing by evaporation the epihalohydrin or the 2-methyl-epihalohidrin from the refined liquid obtained in step (C), thereby forming tris(2,3-epoxypropyl) isocyanurate or tris(2-methyl-2,3-epoxypropyl) isocyanurate as the purified product.

A method for producing tris(2,3-epoxypropyl) isocyanurate or tris(2-methyl-2,3-epoxypropyl) isocyanurate as a purified product which has an epoxide equivalent of 1.0 to 1.1 times the theoretical epoxide equivalent of the isocyanurate and forms a transparent liquid when molten, comprising steps (A) to (D):

• (A) reacting an epihalohydrin or a 2-methyl-epihalohydrin with isocyanuric acid in a reaction mixture containing the isocyanuric acid and the epihalohydrin or the 2-methyl-epihalohydrin in a ratio of 1 mol of active hydrogen atoms of the isocyanuric acid to 1.2 to 60 mol of the epihalohydrin or the 2-methyl-epihalohydrin, and a catalytic amount of a tertiary amine, a quaternary ammonium base or salt, a tri-substituted phosphine or a quaternary phosphonium salt, thereby forming a reaction product containing a tris(2-hydroxy-3-halopropyl) isocyanurate or a tris(2-hydroxy-2-methyl-3-halopropyl) isocyanurate,
• (B) adding gradually to the reaction product an alkali metal hydroxide in a ratio of 1 to 2 mol of the hydroxide to 1 mol of active hydrogen atoms of the isocyanuric acid in the reaction product before the reaction in step (A) to cause and complete dehydrohalogenation to the isocyanurate while agitating the resulting slurry containing a precipitated alkali metal halide, thereby forming a final slurry containing tris(2,3-epoxypropyl) isocyanurate or tris(2-methyl-2,3-epoxypropyl) isocyanurate and an alkali metal halide produced by the reaction,
• (C) washing with water a liquid product obtained by removing the alkali metal halide from the final slurry in step (B) by a process comprising introducing into a column of the liquid product water droplets having a mean a diameter of 0.1 to 10 mm, allowing the droplets to ascend and thereafter to unify to form an aqueous layer in the column, repeating stepwise the cycle consisting of the introducing, the ascending and the unification of the droplets in the column, and continuing supplying to the liquid product water by the introduction thereof until 50 to 5000 parts by weight of the water relative to 100 parts by weight of the isocyanurate in the liquid product is supplied to the liquid product, thereby forming a refined liquid containing the isocyanurate, and
• (D) removing by evaporation the epihalohydrin or the 2-methyl-epihalohidrin from the refined liquid obtained in step (C), thereby forming tris(2,3-epoxypropyl) isocyanurate or tris(2-methyl-2,3-epoxypropyl) isocyanurate as the purified product.

A method for producing tris(2,3-epoxypropyl) isocyanurate or tris(2-methyl-2,3-epoxypropyl) isocyanurate as a purified product which has an epoxide equivalent of 1.0 to 1.1 times the theoretical epoxide equivalent of the isocyanurate and forms a transparent liquid when molten, comprising steps (A) to (D):

• (A) reacting an epihalohydrin or a 2-methyl-epihalohydrin with isocyanuric acid in a reaction mixture containing the isocyanuric acid and the epihalohydrin or the 2-methyl-epihalohydrin in a ratio of 1 mol of active hydrogen atoms of the isocyanuric acid to 1.2 to 60 mol of the epihalohydrin or the 2-methyl-epihalohydrin, and a catalytic amount of a tertiary amine, a quaternary ammonium base or salt, a tri-substituted phosphine or a quaternary phosphonium salt, thereby forming a reaction product containing the resulting tris(2-hydroxy-3-halopropyl) isocyanurate or tris(2-hydroxy-2-methyl-3-halopropyl) isocyanurate,
• (B) adding gradually to the reaction product an alkali metal hydroxide in a ratio of 1 to 2 mol of the hydroxide to 1 mol of active hydrogen atoms of the isocyanuric acid in the reaction product before the reaction in step (A) to cause and complete dehydrohalogenation to the isocyanurate while agitating the resulting slurry containing a precipitated alkali metal halide, thereby forming a final slurry containing tris(2,3-epoxypropyl) isocyanurate or tris(2-methyl-2,3-epoxypropyl) isocyanurate and an alkali metal halide generated by the reaction,
• (C) washing with water the final slurry in step (B) or a liquid product obtained by removing the alkali metal halide from the final slurry in step (B), thereby forming a refined liquid containing the isocyanurate, and
• (D) removing the epihalohydrin or the 2-methyl-epihalohydrin from the refined liquid obtained in step (C), by a process comprising forming by coating on a surface of a substrate a film of the refined liquid or the concentrate thereof having a thickness of 30 to 500 .mu.m and having at one end of the film the highest concentration and gradually lowered concentration toward the lowest concentration at the opposite end of the film respectively of the volatile components in the refined liquid or the concentrate thereof, and evaporating from the film the volatile components under a pressure of 5 mmHg or lower of the components at 100.degree. to 165.degree. C., while supplying continuously to the end of the film having the highest concentration of the volatile components the refined liquid or the concentrate thereof, conveying gradually toward the opposite end the liquid under the evaporation and the film thickness, and recovering continuously from the opposite end of the film a final liquid having a lowered concentration of the volatile components, thereby forming tris(2,3-epoxypropyl) isocyanurate or tris(2-methyl-2,3-epoxypropyl) isocyanurate as the purified product.

A method for producing bis(2,3-epoxypropyl) terephthalate or bis(2-methyl-2,3-epoxypropyl) terephthalate as a purified product which has an epoxide equivalent of 1.0 to 1.1 times the theoretical epoxide equivalent of the terephthalate and forms a transparent liquid when molten, comprising steps (A) to (D):

• (A) reacting an epihalohydrin or a 2-methyl-epihalohydrin with terephthalic acid in a reaction mixture containing the terephthalic acid and the epihalohydrin or the 2-methyl-epihalohydrin in a ratio of 1 mol of active hydrogen atoms of the terephthalic acid to 1.2 to 60 mol of the epihalohydrin or the 2-methyl-epihalohydrin, and a catalytic amount of a tertiary amine, a quaternary ammonium base or salt, a tri-substituted phosphine,a quaternary phosphonium salt or an alkali metal halide, thereby forming a reaction product containing a bis(2-hydroxy-3-halopropyl) terephthalate or a bis(2-hydroxy-2-methyl-3-halopropyl) terephthalate,
• (B) adding gradually to the reaction product in a vessel an alkali metal hydroxide as an aqueous solution having a concentration of 20 to 70 wt % of the hydroxide in a ratio of 1 to 2 mol of the hydroxide to 1 mol of active hydrogen atoms of the terephthalic acid in the reaction product before the reaction in step (A) to cause and complete dehydrohalogenation to the terephthalate in the reaction product and to form a slurry containing a precipitated alkali metal halide, while maintaining the slurry under agitation which causes the slurry to produce a stream circulating and ascending from the bottom along the inner side wall of the vessel to the surface of the slurry, turning there the ascending stream to a stream swirling downward and shearing across the swirling stream, thereby maintaining the slurry uniform, and removing by evaporation from the slurry the water added and caused by the reaction under a vacuum at a temperature of 10.degree. to 80.degree. C., thereby forming a final slurry containing bis(2,3-epoxypropyl) terephthalate or bis(2-methyl-2,3-epoxypropyl) terephthalate and an alkali metal halide generated by the reaction,
• (C) washing with water the final slurry in step (B) or a liquid product obtained by removing the alkali metal halide from the final slurry in step (B), thereby forming a refined liquid containing the terephthalate, and
• (D) removing by evaporation the epihalohydrin or the 2-methyl-epihalohidrin from the refined liquid obtained in step (C), thereby forming bis(2,3-epoxypropyl) terephthalate or bis(2-methyl-2,3-epoxypropyl) terephthalate as the purified product.

A method for producing bis(2,3-epoxypropyl) terephthalate or bis(2-methyl-2,3-epoxypropyl) terephthalate as a purified product which has an epoxide equivalent of 1.0 to 1.1 times the theoretical epoxide equivalent of the terephthalate and forms a transparent liquid when molten, comprising steps (A) to (D):

• (A) reacting an epihalohydrin or a 2-methyl-epihalohydrin with terephthalic acid in a reaction mixture containing the terephthalic acid and the epihalohydrin or the 2-methyl-epihalohydrin in a ratio of 1 mol of active hydrogen atom of the terephthalic acid to 1.2 to 60 mol of the epihalohydrin or the 2-methyl-epihalohydrin, and a catalytic amount of a tertiary amine, a quaternary ammonium base or salt, a tri-substituted phosphine, a quaternary phosphonium salt or an alkali metal halide, thereby forming a reaction product containing a bis(2-hydroxy-3-halopropyl) terephthalate or a bis(2-hydroxy-2-methyl-3-halopropyl) terephthalate,
• (B) adding gradually to the reaction product an alkali metal hydroxide in a ratio of 1 to 2 mol of the hydroxide to 1 mol of active hydrogen atoms of the terephthalic acid in the reaction product before the reaction in step (A) to cause and complete dehydrohalogenation to the terephthalate while agitating the resulting slurry containing a precipitated alkali metal halide, thereby forming a final slurry containing bis(2,3-epoxypropyl) terephthalate or bis(2-methyl-2,3-epoxypropyl) terephthalate and an alkali metal halide generated by the reaction,
• (C) washing with water a liquid product obtained by removing the alkali metal halide from the final slurry in step (B) by a process comprising introducing into a column of the liquid product water droplets having a mean diameter of 0.1 to 10 mm, allowing the droplets to ascend and thereafter to unify to form an aqueous layer in the column, repeating stepwise the cycle consisting of the introducing, the ascending and the unification of water droplets in the column, and continuing supplying to the liquid product water by the introduction thereof until 50 to 5000 parts by weight of water to 100 parts by weight of the terephthalate in the liquid product is supplied to the liquid product, thereby forming a refined liquid containing the terephthalate, and
• (D) removing by evaporation the epihalohydrin or the 2-methyl-epihalohidrin from the refined liquid obtained in step (C), thereby forming bis(2,3-epoxypropyl) terephthalate or bis(2-methyl-2,3-epoxypropyl) terephthalate as the purified product.

A method for producing bis(2,3-epoxypropyl) terephthalate or bis(2-methyl-2,3-epoxypropyl) terephthalate as a purified product which has an epoxide equivalent of 1.0 to 1.1 times the theoretical epoxide equivalent of the terephthalate and forms a transparent liquid when molten, comprising steps (A) to (D):

• (A) reacting an epihalohydrin or a 2-methyl-epihalohydrin with terephthalic acid in a reaction mixture containing terephthalic acid and the epihalohydrin or the 2-methyl-epihalohydrin in a ratio of 1 mol of active hydrogen atoms of the terephthalic acid to 1.2 to 60 mol of the epihalohydrin or the 2-methyl-epihalohydrin, and a catalytic amount of a tertiary amine, a quaternary ammonium base or salt, a tri-substituted phosphine, a quaternary phosphonium salt or an alkali metal halide, thereby forming a reaction product containing a bis(2-hydroxy-3-halopropyl) terephthalate or a bis(2-hydroxy-2-methyl-3-halopropyl) terephthalate,
• (B) adding gradually to the reaction product an alkali metal hydroxide in a ratio of 1 to 2 mol of the hydroxide to 1 mol of active hydrogen atoms of the terephthalic acid in the reaction product before the reaction in step (A) to cause and complete dehydrohalogenation to the terephthalate while agitating the resulting slurry containing a precipitated alkali metal halide, thereby forming a final slurry containing bis(2,3-epoxypropyl) terephthalate or bis(2-methyl-2,3-epoxypropyl) terephthalate and an alkali metal halide generated by the reaction,
• (C) washing with water the final slurry in step (B) or a liquid product obtained by removing the alkali metal halide from the final slurry in step (B), thereby forming a refined liquid containing the terephthalate, and
• (D) removing the epihalohydrin or the 2-methyl-epihalohidrin from the refined liquid obtained in step (C), by a process comprising forming by coating on a surface of a substrate a film of the refined liquid or the concentrate thereof having a thickness of 30 to 500 .mu.m and having at one end of the film the highest concentration and gradually lowered concentration toward the lowest concentration at the opposite end of the film respectively of the volatile components in the refined liquid or the concentrate thereof, and evaporating from the film the volatile components under a pressure of 5 mmHg or lower of the components at 100.degree. to 165.degree. C., while supplying continuously to the end of the film having the highest concentration of the volatile components the refined liquid or the concentrate thereof, conveying gradually toward the opposite end the liquid under the evaporation and the film thickness, and recovering continuously from the opposite end of the film a final liquid having a lowered concentration of the volatile components, thereby forming bis(2,3-epoxypropyl) terephthalate or bis(2-methyl-2,3-epoxypropyl) terephthalate as the purified product.