TW487697B - Method for producing purified epoxy compound - Google Patents

Abstract

A 2,3-epoxypropyl derivative or a 2-methyl-2,3-epoxypropyl derivative of a compound having carboxyl groups or amido groups is produced as a purified product having an epoxide equivalent of 1.0 to 1.1 times the theoretical epoxide equivalent of the derivative, an ionic halogen content of 10 ppm or less, transparency when molten and a stability against increase in the epoxide equivalent when stored at 150 DEG C for 24 hours, by a process comprising steps (A) reacting 1.2 to 60 mol of an epihalohydrin or a 2-methyl-epihalohydrin with 1 mol of active hydrogen atoms of the carboxyl or amido group of the compound in the presence of a catalytic amount of a tertiary amine, a quaternary ammonium base or salt, a tri-substituted phosphine or quaternary phosphonium salt, thereby forming a reaction product containing a 2-hydroxy-3-halopropyl derivative or a 2-hydroxy-2-methyl-3-halopropyl derivative, (B) dehydrohalogenating the derivative by adding to the reaction product a sufficient amount of an alkali metal hydroxide while agitating the resulting slurry containing a precipitated alkali metal halide, thereby forming a final slurry containing the 2,3-epoxypropyl derivative or the 2-methyl-2,3-epoxypropyl derivative and the alkali metal halide, (C) washing the final slurry or a liquid product formed by removing the alkali metal halide from the final slurry with an aqueous solution of, as refining agent, a sulfonic acid, a salt of a sulfonic acid, a salt of a carboxylic acid having at least 7 carbon atoms, a salt of a sulfate of an alcohol having at least 4 carbon atoms or a mixture thereof respectively having a solubility of at most 1 wt% in water at 30 DEG C containing the refining agent in an amount effective to refine the slurry or the liquid product, thereby forming a refined liquid containing the derivative, and (D) removing by evaporation the epihalohydrin or the 2-methyl-epihalohidrin from the refined liquid, thereby forming the 2,3-epoxypropyl derivative or the 2-methyl-2,3-epoxypropyl derivative as the purified product.

Description

487697 A7 B7 V. Description of the invention (1) The present invention relates to an improved method for producing a purified product of an epoxy compound having 2,3-epoxypropyl group or 2-methyl-2,3-epoxypropyl group, especially Related to the effective production of 2,3-epoxypropyl derivatives or 2-methyl-2,3-epoxypropyl derivatives from compounds having 2 to 4 carboxyl groups or 1 to 3 amido groups in the molecule, of which All hydrogen atoms in the carboxyl or amido group are replaced by a 2,3-epoxypropyl group or a 2-methyl-2,3-epoxypropyl group to a purified product which forms a transparent and stable liquid when molten. u · S · P · 3, 8 5 9, 3 1 4 discloses a method for manufacturing a glycidyl ester of a polycarboxylic acid, which comprises combining a polycarboxylic acid (carboxyl group per polycarboxylic acid) with at least 2 molar epichlorohydrin The reaction uses a tertiary amine, a tertiary amine salt or a quaternary ammonium compound as a catalyst, the temperature of which is from 150 to 200 ° F, until the acid value is 0, and then is generated when it is enough to evaporate to remove dehydrohalogenation. At 90 to 130 ° F of water under reduced pressure, an alkali metal hydroxide was gradually added to the ester to dehydrotarrate the formed dentitol ester. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) The description of the patent reveals an example in which the epoxy equivalent is 15 2 and the total chlorine content is 0.8%. Diglycidyl phthalate is produced by a method that includes washing the product formed by the dehydrohalogenation of a chlorohydrin ester of an isoacid with water, and then distilling off the epichlorohydrin of the product under reduced pressure. This oxygen equivalent is 1.09 times larger than the theoretical value of 139. Japanese Examined Patent Publication JP — B — 44 — 2 0 3 2 3 discloses a method for producing an N-glycidyl derivative having a fluorenyl compound, which comprises reacting the fluorenyl compound with a fluorenyl group under a dentine scale. The reaction product formed is then treated with a base compound. The announcement revealed in the example that the triglycidyl isocyanurate product with a yield of 89% is based on water. The paper standard is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) 487697 A7 B7

Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (2) 'Sodium dihydrogen phosphate aqueous solution, and then the product produced by this method was washed with distilled water' followed by removal of the washed product under reduced pressure at 110 ° C Volatile components, the final product is obtained by crystallizing a 50 wt% methanol solution of the product with an epoxy equivalent of 0.92 per 100 g of the product and a chlorine content of 1.0 wt%. When heated at 100 ° C for 115 hours, the epoxy equivalent of the final product decreased by 10%. The patent of this trial patent: [p-B — 45 — 2275 1 discloses a method for producing triglycidyl isocyanurate, which comprises contacting cyanic acid with 6 to 30 times the molar amount of epichlorohydrin in the presence of Medium, such as tertiary amine, quaternary ammonium base and quaternary ammonium salt, react at 60 to 165 ° C, add 5 to 40% stoichiometric excess of a concentrated alkali metal hydroxide aqueous solution, water, two An aqueous solution of sodium hydrogen phosphate or a diluted aqueous solution of sodium hydroxide and finally the reaction product formed by washing with water in a stirred state are then used to remove epichlorohydrin using a rotary evaporator. In the example of this application, it is revealed that the product contains from 9.4 to 9.8 mol of ethylene oxide oxygen per 1 kg and from 0.5 to 1.1% of chlorine. USP 3,198,241 discloses a method for separating and recovering a non-volatile substance from a mixture of non-volatile substances and volatile substances in a fluid, which comprises flowing the fluid by gravity on a vertical heat transfer plate surface and passing the fluid through a heat exchange medium. The heat transfer from the flowing fluid film evaporates the volatile substance to repeatedly form a thin film of the fluid. U.S.P. 4,39 5,542 discloses a method in which triglycidyl isocyanurate containing at least 2000 p ppm epichlorohydrin and accompanying volatile substances is heated enough to make the isocyanurate Cyanuric acid triglycidine pack (Please read the precautions on the back before filling this page) Order # This paper size applies to China National Standard (CNS) A4 (210X297 mm) -5-

487697 A7 B7 printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (3) Oil esters are fluidized, but not enough to cause pyrolysis temperatures, such as from 1 4 3 to 159 ° C, and then passed by gravity A column with a fine mesh sieve, or a multi-stage stripping at least once through a multi-stage stripper at a pressure of 1 to 50 Omni H g, to produce at least 10 ppm PM epichlorohydrin and related volatile substances. Triglycidyl isocyanurate. The epoxy compounds produced by these conventional methods can be used for general purposes, such as raw materials for polyester coatings. However, there is an increased demand for these epoxy compounds in the form of high purity industrial products for certain purposes. In particular, epoxy compounds used as sealants, conductive adhesives, and solder resists for semiconductors must provide polycarboxylic acids in the form of high-purity industrial products that are suitable for these applications and have at least one amido group in the molecule. Or a compound of 2,3-epoxypropyl derivative or 2-methyl-2,3-epoxypropyl derivative. The combination of the above-mentioned conventional manufacturing methods and known purification methods can provide a certain degree of high purity requirements. For example, 'Epichlorohydrin solution of 2,3-epoxypropyl derivative prepared by the above method repeatedly washed with water, or 2-methyl epichlorohydrin of 2-methyl-2,3-epoxypropyl derivative. Alcohol solutions, or 2,3-epoxypropyl derivatives or 2-methyl-2,3-epoxypropyl derivatives of these conventional methods products recrystallized from alcohols such as methanol, which are recrystallized The purity can be improved. However, because these glycidyl esters and N-glycidyl compounds are usually dissolved in water in a negligible amount, when washing with water ', repeated washing with water as described above results in a low yield of the product. The purification method of recrystallization described above is not applicable to the amorphous phase epoxy compound product. This method is applicable to the paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) V 1 · Packing · (Please read the precautions on the back before filling this page)

1T 6-487697 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (4) When crystalizing the epoxy compound product, it is difficult to remove the fine insoluble impurities in the product, and this method cannot achieve the Thorough purification of transparent melt when the product melts. In the manufacturing method disclosed in Japanese Examined Patent Publication J P — B — 45-2275 1 because of the use of a rotary evaporator, epichlorohydrin removal is not effective in this method, and the yield of the product is quite low. Therefore, this method is not conducive to mass production. In the method disclosed in Japanese Examined Patent Publication JP — B — 44 — 2 0 3 2 3, the final epichlorohydrin removal effect of the method is removed by evaporation under reduced pressure, but this announcement does not disclose improvement of product purity Method. In the method disclosed by U.S.P. 3, 1 98, 24 1, because the flowing down fluid film is formed by gravity flowing down, such as high viscosity of isocyanuric acid triglycidylol containing low concentration epichlorohydrin. It is difficult for the fluid to form a thin film in a short time. In the method disclosed in the U.S. patent, a fluid film must be repeatedly formed at high temperature multiple times. Therefore, it does not take a long time to remove epichlorohydrin, and the purity of the product may decrease when the product maintains these high temperatures for a long time. In the method disclosed by U.S.P. 4,39 5,542, because the flow system is flowing down due to gravity, high viscosity fluids such as isocyanurate triglycidyl esters containing low concentrations of epichlorohydrin cannot flow down. A thin film is formed. Compared with U.S.P. 3,198,241, the method of forming a downflow fluid film, the multi-stage stripping evaporation method can remove epichlorohydrin in a short time. However, high molecular weight compounds will adhere to the inner wall of the stripper, thus hindering smooth heat transfer, or the product will be insoluble after stripping. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). 7-- Equipment-(Please read the precautions on the back before filling this page) Order 487697 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (5) Material pollution, especially in large-scale installations very. In particular, products containing such insoluble substances cause problems such as low transparency of the molded article when molded as a transparent resin molded article, and poor smoothness of the surface of a coating film when used as a paint. The object of the present invention is to propose a method for efficiently producing a 2,3-epoxypropyl derivative or a 2-methyl-2,3-cyclo ring from a compound having 2 to 4 carboxyl groups or 1 to 3 amido groups in the molecule. Method for oxypropyl derivative, in which all hydrogen atoms in the carboxyl group or amido group are substituted by 2,3-epoxypropyl group or 2-methyl-2,3-epoxypropyl group, which is an industrial product, Ethylene oxide has a high oxygen content, high thermal stability and low ion content, and forms a transparent liquid when melted. The invention proposes a method for producing a purified product of a 2,3-epoxypropyl derivative or a 2-methyl-2,3-epoxypropyl derivative having 2 to 4 carboxyl groups or 1 to 3 amidino groups. , Its epoxy equivalent is 1 · 0 to 1 · 1 times the theoretical epoxy equivalent of the derivative. The ionic halogen content is 10 ppm or less. It forms a transparent liquid when melted. When it is stored at 150 ° C for 24 hours, the epoxy equivalent increases up to 3%. The method includes steps (A) to (D): (A ) Reacting epihalohydrin or 2-methyl-epihalohydrin with a compound having 2 to 4 carboxyl groups or 1 to 3 amido groups in the molecule, the reaction mixture containing the compound and the epihalohydrin or 2-methyl -Epihalohydrin in a ratio of 1 mole of active hydrogen atom of the carboxyl group or amido group of the compound to 1.2 to 60 moles of epihalohydrin or 2-methyl-epihalohydrin, and a catalytically effective amount Tertiary amine, quaternary ammonium base or salt, tertiary substituted phosphine or quaternary scale salt, so (please read the precautions on the back before filling this page) The scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -8-487697 A7, B7 V. Description of the invention (6) Formation of the compound containing 2-hydroxy-3 -halopropyl derivative or 2-hydroxy-1 2 —Methyl-3—halopropyl derivative, (B) Alkali metal hydroxide is gradually added to the reaction product at a ratio of 1 to 2 moles of hydrogen The active hydrogen atom of the carboxyl or amido group of the compound in the reaction product before the reaction of the oxide with 1 mol step (A) to initiate and complete the dehydrohalogenation of the derivative, and the formed alkali metal halide containing the precipitate is stirred and formed The slurry thus forms a final slurry containing the compound 2,3-epoxypropyl derivative or 2-methyl-2,3-epoxypropyl derivative, and an alkali metal halide produced by dehydrohalogenation. (C) The solubility of sulfonic acid, sulfonate, carboxylic acid having at least 7 carbon atoms in the molecule, sulfate ester of alcohol having at least 4 carbon atoms in the molecule, or a mixture thereof in water at 30 ° C, respectively. At least 1% by weight, as an aqueous solution of the refined preparation, the final slurry prepared in the cleaning step (B) or a liquid product prepared by removing the alkali metal halide from the final slurry in the step (B), the content of the refined preparation in the solution may be Effectively refining the slurry or liquid product, so as to form a refined liquid containing the derivative formed in step (B), and printed by a consumer consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs-(Please read the precautions on the back before filling in this Page) 4 (D) Evaporation to remove epihalohydrin or 2-methyl-epihalohydrin from the refined liquid obtained in step (C), thus forming the compound 2,3-epoxypropyl derivative or 2-methyl A purified product of the phenyl-2,3-epoxypropyl derivative. In the present invention, the epoxy equivalent of a product of an epoxy compound is defined as the weight (in grams) of the product containing 1 mole of ethylene oxide oxygen atom. The ionic tooth element content of the product is determined by ion chromatography of the sample solution of the product. The paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm)-9-487697 A7 B7. 5. Description of the invention (7) Analysis and measurement, It dissolves the product in a liquid mixture of 100 parts by weight of acetonitrile and 25 parts by weight of pure water, or extracts the product with the liquid mixture, and indicates the content of the ionodentin in the product in the form of a salt. . The thermal stability of the product is represented by the percentage of the epoxy equivalent of the product before and after heating at 150 ° C for 24 hours in a sealed container. The smaller the percentage increase in epoxy equivalent, the higher the thermal stability of the product is estimated. The turbidity of the product melt is represented by the turbidity of the melted kaolin after degassing. The definition of kaolin turbidity is when 1 g of a mixture of guaranteed grade kaolin and 10 m H 37wt% formaldehyde water is diluted with pure water, 10 p pm kaolin solution is grade 1, 2 p p kaolin is grade 2, 30 ppm Kaolin is grade 3 and 50 ppm kaolin solution is grade 4. The kaolin turbidity of the product melt was evaluated based on the kaolin turbidity of a kaolin solution of the same turbidity. The smaller the kaolin turbidity of the product melt, the higher the purity of the product. Products with a kaolin turbidity of 1 or less are roughly transparent. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) The product obtained in the above step (D) of the present invention is a highly purified product, and its epoxy equivalent is the theoretical epoxy of the derivative 1 to 1 times the equivalent, thermal stability is equivalent to an epoxy equivalent increase of up to 3%, ionic halogen content is 10 p pm or less, and the kaolin turbidity is at most 1 when melted. The original compound having 2 to 4 carboxyl groups in the molecule supplied in the step (A) may be any compound which is a conventional epoxy compound raw material. For example, aliphatic dicarboxylic acids such as maleic acid, succinic acid, decomposed aconitic acid, fumaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, or self-unsaturated Standard (CNS) A4 specification (210X297 mm)-10-Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 487697 \ A7 B7 V. Description of the invention (8) Fatty acid-derived dimer or trimer acid; aromatic dicarboxylic acid Acids, such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hy mic acid, tetrachlorophthalic acid, hexahydrophthalic acid, phenylenediacetic acid, or fruit dicarboxylic acid; aromatic tricarboxylic acids, Such as trimellitic acid or trimellitic acid; and aromatic tetracarboxylic acids such as trimellitic acid. Because a carboxyl group has one active hydrogen atom, dicarboxylic acid, tricarboxylic acid, and tetracarboxylic acid, each molecule has 2, 3, and 4 active hydrogen atoms. As long as the acid anhydride reaction derived from a compound having a carboxylic acid group is the same as the compound having a carboxyl group used in step (A), it may be used. The active hydrogen atom of one molecule of these anhydrides is represented by the total number of carboxyl groups in one molecule of the anhydride hydrolysis product. Preferred examples of the compound having 2 to 4 carboxyl groups are phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic acid, and pyromellitic acid. As the compound having 1 to 3 amidino groups in the molecule, a compound conventionally used as a raw material of an epoxy compound can be used. For example, the presenters are N, _N /-dimethylurea, N, N > --diphenylurea, norylurea, hydantoin and isocyanuric acid. Among them, hydantoin and isocyanuric acid are preferred. Ethylurea, N, N < -dimethylurea and N, N, -diphenylurea each have one amido group and two active hydrogen atoms. Hydantoin has two amido groups and two active hydrogen atoms. Isocyanuric acid has three amido groups and three active hydrogen atoms. As the epihalohydrin, epichlorohydrin, epibromohydrin, and epiiodohydrin can be mentioned. Of these, epichlorohydrin is preferred because it is easily available. As the 2-methylepihalohydrin, 2-methylepichlorohydrin, 2-methylepibromohydrin, and 2-methylepiodohydrin can be proposed. From the standpoint of availability, 2-methylepichlorohydrin is preferred. Amine, quaternary ammonium compound, substituted phosphine, quaternary ammonium compound can be used. The paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm). Packing-(Please read the precautions on the back before filling this page. ) Order -11-487697 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. The invention description (9) etc. is used as the catalyst. Although primary amines such as butylamine and secondary amines such as dibutylamine can be used, preferred catalysts are tertiary amines, quaternary ammonium bases, quaternary ammonium salts, trisubstituted phosphines, and quaternary scale salts. Preferred catalyst systems are, for example, tertiary amines such as triethylamine, tri-n-propylamine, tributylamine, fluorenyldimethylamine or triethanolamine; quaternary ammonium hydroxides such as tetramethylammonium hydroxide or benzyl Trimethylammonium hydroxide; quaternary ammonium salts, such as fluorenyltrimethylammonium chloride, benzyltrimethylammonium acetate, methyltriethylammonium chloride, tetramethylammonium chloride or tetraethylammonium chloride; three substituted phosphines , Such as triphenylphosphine, tricresylphosphine or tributylphosphine; and quaternary scale salts, such as methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, methyltriphenylphosphonium iodide, Fluorenyl triphenyl bromide or ethyl triphenyl bromide. Above, tetramethylammonium chloride, tetraethylammonium bromide, and ethyltriphenyl bromide are preferred. When terephthalic acid is used as a raw material, an alkali metal halide such as sodium bromide can be used as a catalyst. As examples of alkali metal hydroxides, sodium, potassium, and potassium hydroxides can be mentioned. Among them, sodium hydroxide and potassium hydroxide are preferred. These alkali metal hydroxides are preferably used in the form of a concentrated aqueous solution, for example, at a concentration of 20 to 70 wt%, and more preferably from 40 to 60 wt%. In step (A), four kinds of raw materials can be used. The first is composed of the above-mentioned compounds having a carboxyl group and epidentate alcohol, the second is composed of the above-mentioned compounds having a carboxyl group and 2-methyl epidentate, and the third is composed of the above-mentioned compounds having amidino group and epihalohydrin The fourth compound is composed of the compound having amidino group and 2-methylepihalohydrin. Regardless of which raw material is used, the epihalohydrin or 2-methyl epihalohydrin is used at a ratio of 1.2 to 60 mol, preferably 2 to 20 mol, and most preferably from 5 to 10 mol. For 1 paper size Applicable to China National Standard (CNS) Α4 specification (210 × 297 mm)-installed-(Please read the precautions on the back before filling this page)

1T # -12-487697 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 * ___B7 V. Description of the invention (10) Mole has a compound with a carboxyl group or an active hydrogen atom in an amidine compound. In step (A), the compound having a carboxyl group or amidino group is reacted with epihalohydrin or 2-methylepihalohydrin to form a 2-hydroxy-3 -halopropyl group having a carboxyl or amidino group. Derivatives or 2-hydroxy- 2-methyl- 3-halopropyl derivatives. Therefore, the bis (2-hydroxy-3-halopropyl) ester or the bis (2-hydroxy-2-methyl-3-halopropyl) ester thereof is respectively formed from the dicarboxylic acid as described above, as described in the above three The carboxylic acid forms its tris (2-hydroxy-3-halopropyl ester) or its tris (2-hydroxy-2 2-methyl-1 3-halopropyl) ester, and the tetracarboxylic acid forms its tetra (2- Hydroxy-3 -halopropyl) ester or its tetra (2-hydroxy-2 -methyl-3 -halopropyl) ester. On the other hand, the N, N > -bis (2-hydroxy-3-halopropyl) derivative or its bis (2-hydroxy-2-methyl-3-halopropyl) derivative is formed from the urea derivative as described above. Base) derivative, hydantoin forms its N, N / -bis (2-hydroxy-3-halopropyl) derivative or its bis (2-hydroxy-1 2-methyl-3-halopropyl) derivative And isocyanuric acid to form its tris (2-hydroxy-3-halopropyl) ester or its tris (2-hydroxy-2-methyl-3-halopropyl) ester. Although the addition reaction in step (A) can be performed in the absence of a catalyst, it is better to use a substance that can promote the reaction to promote the reaction. This substance has a wide range of properties, ranging from relatively weak effects such as alkali metal hydroxides (such as sodium hydroxide) to the above-mentioned catalysts with relatively strong effects. However, it is better to use the above-mentioned preferred catalysts to promote the reaction. Therefore, this addition reaction is based on the above raw materials and tertiary amines, quaternary ammonium bases, quaternary ammonium salts, and tertiary warp. The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the back first Please fill in this page again for the matters needing attention)

1T -13-487697 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (11) s Phosphine or quaternary scale salt as the catalyst reaction mixture, under heating (from 60 to 1 3 0 ° C). The catalyst is used in an amount of from 0.001 to 0.1 mole, and preferably from 0.01 to 0.05 mole. The catalyst has a carboxyl or amido-based compound ratio to 1 mole. When terephthalic acid is used as the raw material for the reaction, the above-mentioned molar ratio is also applicable to the alkali metal halide catalyst therein. In the above reaction mixture, at the beginning of the reaction, water containing 0.1 to 2% by weight of epihalohydrin or 2-methylepihalohydrin may be used to promote the reaction. The reaction mixture is heated until at least 90% (preferably all) of the reaction mixture having an active hydrogen atom having a carboxyl group or an amido compound disappears. Active hydrogen atoms in the reaction mixture can be detected, for example, by liquid chromatography. Usually heated for 2 to 10 hours to prepare the reaction product containing epihalohydrin and the above 2-hydroxy-3-halopropyl derivative, or containing the 2-methyl epihalohydrin and the aforementioned 2-hydroxy-1 2-methyl The reaction product of a 3-halopropyl derivative. In step (B), for the reaction product obtained in step (A), 2-hydroxyl-3-halopropyl derivative and by-product 2-hydroxyl-1,3-dihalopropane or 2-hydroxyl-2— A methyl 3-halopropyl derivative and a by-product 2-hydroxy-1 2-methyl-1,3-dihalopropane are dehydrohalogenated to prepare an epoxy compound for removing hydrogen halide. Therefore, in this reaction, the by-products 2-hydroxy-1, 3-dihalopropane form epihalohydrins, and the byproducts 2-hydroxy-1 2-methyl-1 1, 3-dihalopropane form 2-methylepihalol. . On the other hand, the bis (2-hydroxyl paper size produced in step (A) applies to the Chinese National Standard (CNS) A4 specification (210X297 mm). Wide-— Pack-(Please read the precautions on the back first) Refill this page) Order -14-487697 A7 B7 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention (12) 3- (3-halopropyl) ester of dicarboxylic acid to form the bis (2, 3- Glycidyl Ester), and the bis (2-Hydroxy-2, Methyl-3, Halopropyl) Dicarboxylic Acid Ester ) Ester. Similarly, tris (2-hydroxyl-3-halopropyl) tricarboxylic acid esters form the tris (2,3-epoxypropyl) tricarboxylic acid tris, -Methyl 3-halopropyl) ester to form the tris (2-methyl_2,3-epoxypropyl) ester of the tricarboxylic acid. Tetrakis (2-hydroxy-3-halopropyl) tetracarboxylic acid esters are respectively used to form tetra (2,3-epoxypropyl) tetracarboxylic acids, and Methyl-3-halopropyl) ester forms the tetra (2-methyl-2,3-epoxypropyl) ester of the tetracarboxylic acid. N, N > -bis (2-hydroxy-3) of the hydrazone derivative —Halopropyl) derivative to form the N, N > -bis (2,3-epoxypropyl) derivative of the urea derivative, and the N, N / —bis (2-hydroxy-1 2— The methyl-3-halopropyl) derivative forms the N, N / one bis (2-methyl-2,3-epoxypropyl) derivative of the urea derivative. The N, —Bis (2-hydroxyl-3-halopropyl) derivative to form N, N of hydantoin > —Bis (2,3-epoxypropyl) derivative and N, N from hydantoin /-Bis (2-methyl-2,3-methyl-halopropyl) derivative to form N, bis (2-methyl-2,3-epoxypropyl) derivative. Isocyanuric acid is formed from three (2-hydroxy-3-halopropyl) esters of isocyanuric acid Tris (2,3 - epoxypropyl) isocyanurate, isocyanuric acid, and (Read back surface of precautions - broad J # - refill items, means: - write page)

、 1T 4 This paper size applies Chinese National Standard (CNS) A4 specification (210X297mm) 15-487697 A7 B7 V. Description of the invention (13) tertiary (2-Hydroxy-2 -methyl-3 -halopropyl) ) Esters form tris (2-methyl-2,3-epoxypropyl) isocyanurate. In step (B), the reaction product obtained in step (A) is gradually added (preferably added dropwise) an alkali metal hydroxide 20 to 70 wt% aqueous solution, preferably 40 to 60 wt% More preferably, the ratio is 1 to 2 moles of hydroxide (preferably 1 to 1.2 moles) to the active hydrogen atom of 1 mole of carboxyl group or amido group in the reaction product before the addition reaction, so that Epichlorohydrin or 2-methylepichlorohydrin in the reaction product was refluxed. The above-mentioned dehydrogenation reaction occurs when an alkali metal hydroxide is added, and an alkali metal halide and water are generated in the reaction mixture. The alkali metal compound is crystallized to prepare a slurry containing an alkali metal halide which has been precipitated. The dehydrohalogenation reaction can be accelerated in the presence of an aprotic polar solvent (such as dimethylformamide or methyl isobutyl ketone) in the presence of 5 to 3 Owt% of the epichlorohydrin in the slurry. Reduce the content of hydrolyzed halogen in the product obtained in the subsequent step (D). When the reaction is carried out in the presence of the above-mentioned aprotic polar solvent, although the solvent may be added to the reaction mixture of step (A) in advance, it is better to add the solvent to the slurry of step (B), which is carried out at a relatively low temperature Speed up the reaction. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page). When the slurry is formed, keep the slurry as low as possible under reduced pressure, such as from 10 to 80 ° C It is better to use 20 to 7 ΐ ΐ, to continuously evaporate the added water and the water generated with the epihalohydrin or the 2-methylepihalohydrin in the slurry, and the vapor is condensed by a condenser from the reaction mixture. Drain the condensed water and return the condensed epihalohydrin or 2-ethylepihalohydrin to the slurry. In addition, the vacuum at the beginning of the adding period is maintained at about 100 to allow H g, and then the degree of vacuum is gradually increased with the adding effect to the paper size. The Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applied. -16-487697 A7 B7 V. Description of the invention (14) In the end, about 60 mm Hg is better. The reaction of step (B) is usually completed within 1 to 10 hours. The reaction of step (B) is preferably carried out under stirring of the slurry. When the reaction is performed on a small scale, for example, ordinary stirring using a paddle or a turbine is satisfactory. However, when the reaction of step (B) is performed on a large scale, such as a slurry having a volume of at least 20 j ?, ordinary stirring is not applicable. If the stirring action is not appropriate, the precipitated alkali metal halide, water, and alkali metal hydroxide may accumulate or adhere to the bottom or wall of the container, and the fluid may not flow smoothly, thus preventing the water from smoothly evaporating. Such improper dispersion of precipitated alkali metal halides, water and alkali metal hydroxides can easily cause side reactions where they accumulate, resulting in low yields and low purity of the products obtained in subsequent steps (C) and (D). However, it has been found that high levels of product yield and purity can be maintained when the slurry is maintained in a stirred state sufficient to avoid accumulation of precipitated alkali metal halide, water, and alkali metal hydroxide. High-speed rotation of a stirrer equipped with blades or turbine blades alone cannot effectively prevent the slurry (especially a large amount of slurry of at least 100 P) from accumulating metal halides, water, and metal halide hydroxides. When the reaction proceeds, the precipitation of the alkali metal halide in the slurry is increased to a high concentration, which is sufficient to generate great resistance to the high-speed rotating stirrer. Sometimes these high-speed rotating agitators finally press only the precipitated alkali metal halide, water and alkali metal hydroxide to the wall of the container. In addition, in a large number of slurry examples, the water in the slurry can easily evaporate from the surface near the slurry, but it is difficult to boil at the bottom of the reaction vessel. Therefore, if alkali metal halides, water and alkali metal hydroxides are still located at the bottom of the reaction container after being precipitated, it is easy to produce copies in the slurry. Paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) (please first Notes on the back of the book ---: Write this page) Order printed by the Central Consumers ’Cooperative of the Ministry of Economic Affairs -17-W87697 A7 B7 Printed by the Central Consumers’ Cooperative of the Ministry of Economic Affairs ’Consumer Cooperatives It is not extremely important to cause the slurry to flow at a high speed, and the stirring effect to cause the slurry to locally circulate is also inefficient. Instead, an agitating effect that uniformly disperses the slurry as a whole is preferred. A preferred stirring action is, for example, to cause the slurry to generate a circulating flow from the bottom along the inner wall of the container to the surface of the slurry, where the rising flow turns into a vortex downward flow and shears the vortex flow, so that the slurry remains uniform. Agitators that generate such circulating flows and vortex flows and cut the vortex flows into several sections are known and commercially available. A stirrer that performs these better stirring effects and a reaction vessel equipped with a baffle plate can provide better stirring effects when used in combination. Therefore, when step (B) is used to process a large amount of slurry of at least 1 0 0 P in a container by method (B >), wherein method (B >) includes the reaction product prepared in step (A) at a rate of 1 per 1 The compound contains active hydrogen atoms in the reaction product before the addition of Moore. Gradually add 1 to 2 Moore, preferably 1 to 1.2 Moore alkali metal hydroxide. Its aqueous solution concentration is 20 to 70% by weight. Preferably, 40 to 60 wt% hydroxide is used to form a slurry containing the precipitated alkali metal halide and maintain the slurry in a stirred state, which causes the slurry to circulate and rise from the bottom along the inner wall of the container to the surface of the slurry. The upwelling is turned into a vortex downflow, and the vortex is cut, so that the slurry is kept uniform, and the added or generated water is evaporated from the slurry in a vacuum at a temperature of 20 to 60 ° C until the Until the completion of the hydrohalogenation, a 2,3-epoxypropyl derivative and an epihalohydrin containing a compound having a precipitated alkali metal halide and a carboxyl or amido group, or a 2-methyl-2,3 of the compound is formed. -Glycidyl derivative (Please read the back first Notes on filling out this page) 4 • · items reloading equipment _

、 1T # This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 18-487697 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 1 ____ B7 V. Invention Description (16) and 2-A Base epihalohydrin slurry. This method (B /) significantly improves the purity of the product in the subsequent step (E), it significantly reduces the amount of by-product impurities in the reaction product, and is therefore conducive to the manufacture of crystalline derivatives, such as isocyanuric acid three (2, 3-glycidyl ester or tris (2-methyl-2,3-glycidyl) ester, or bis (2,3-glycidyl) ester of phthalic acid or bis (2-formyl) -2,3-epoxypropyl) ester. As the refined preparation used in step (C), a water-soluble organic group-containing compound having a solubility of at least 1 wt% in water at 30 ° C can be used. If an organic-based compound with a solubility of less than 1 wt% in water at 30 ° C is used as a refined preparation, the low-solubility compound in the aqueous solution will move to the adjacent organic layer and remain in the product collected in the subsequent step, reducing the quality of the product . Although the increase in the number of carbon atoms in the organic group of this compound will cause the solubility of the organic group-containing compound to decrease, it is not preferable to use a compound containing an organic group and having a solubility of at least 1 wt% in 30 ° C water. If the yield or efficiency of the product caused by the additional cleaning step is within a tolerable range, a compound prepared by dissolving in water to make an acidic or alkaline aqueous solution can be used as a refining compound, but a compound prepared by dissolving in water to make a neutral aqueous solution. It is better because it does not cause such a decrease in efficiency. Sulfonates, sulfonates, carboxylates, sulfates of alcohols, or mixtures thereof can be mentioned as the compound of the preparation. These compounds may include a hydrocarbon group, amidino group, an ester group, a hydroxyl group, an ether group, an ethoxy group, or a hydrocarbon group substituted with these groups. Among the above-mentioned salts, monobasic alkali salts which can make the salt highly soluble, such as salts of alkali metals such as sodium, potassium, or lithium, salts of amines such as monoethanolamine, diethanolamine, or triethanolamine, or ammonium salts are preferred, It is superior to polybasic alkalis such as magnesium. The paper size applies Chinese National Standard (CNS) A4 specifications (210'〆297 mm) <-Packing · (Please read the precautions on the back before filling this page) Order-19- 487697 A7 B7 printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (17) Calcium or aluminum salts. Preferable examples of the sulfonic acid include benzenesulfonic acid 'substituted with benzenesulfonic acid having an alkyl group having 1 to 3 carbon atoms, such as toluenesulfonic acid and xylenesulfonic acid, and tartaric acid. Preferred examples of sulfonates are alkali metal, ammonium or amine salts of aromatic sulfonic acids, such as alkali metal salts (such as sodium salts), ammonium or amine salts (such as triethanolamine salts) of benzenesulfonic acid. Alkyl substituted benzene mineral acids of 1 to 3 carbon atoms, such as alkali metal salts (such as sodium salts), ammonium salts, or amine salts (such as triethanolamine salts) of toluene sulfonic acids. Formaldehyde condensate, alkali metal salt (such as sodium salt), ammonium or amine salt (such as triethanolamine salt) of p-hydroxybenzenesulfonic acid, alkali metal salt (such as sodium salt), ammonium salt or Amine salts (such as triethanolamine salts), alkali metal salts (such as sodium salts), ammonium or amine salts (such as triethanolamine salts) of fruit sulfonic acids, or alkali metal salts of aromatic sulfonic acids, such as sulfonium sulfonates Formaldehyde condensate; ammonium alkanesulfonate or amine salt with up to 10 carbon atoms 'for example, an alkali metal salt (such as sodium salt), ammonium or amine salt (such as triethanolamine salt) of methane expansion acid' Alkali metal salts of acids (such as sodium salts), phosphonium salts or amine salts (such as triethanolamine salts), vinyl sulfonate Alkali metal salts (such as sodium salts), ammonium salts or amine salts (such as triethanolamine), polymers of these vinyl sulfonates' alkali metal salts (such as sodium salts) of aminoethane sulfonic acids, Iron or amine salts (such as triethanolamine salts), alkali metal salts (such as sodium salts), ammonium or amine salts (such as triethanolamine salts) of octyl sulfoacetic acid, but alkali metal salts (such as sodium Salt), ammonium salt or amine salt (such as triethanolamine salt) 'alkali metal salt (such as sodium salt), ammonium salt or amine salt (triethanolamine salt) -(Please read the notes on the back before filling out this page) Order 4. Printed by the Central Bureau of Standards of the Ministry of Economic Affairs and Consumer Cooperatives 487697 A7 · B7______ 5. Description of the Invention (is), Alkali metal salt of octane sulfonic acid ( (Such as sodium salt), iron or amine salt (such as triethanolamine salt), alkali metal salt (such as sodium salt), ammonium salt or amine salt (such as triethanolamine salt) of decanoate minerals. An alkali metal salt of Yuanyuan acid having at most 11 carbon atoms, such as an alkali metal salt (such as sodium salt) of heptanoic acid Alkali metal salts of acids (such as sodium salts), or alkali metal salts of capric acid (such as sodium salts); alkali metal salts of aromatic monocarboxylic acids, such as sodium benzoate, sodium salicylate or sodium cinnamate; Alkali metal salts of carboxylic acids such as disodium acid; dibasic metal salts of alicyclic hydrocarbon dicarboxylic acids such as disodium hexahydrophthalate; and alkali metal salts of hydroxybenzenecarboxylic acids such as sodium o-hydroxybenzoate or Paraben sodium. Preferred examples of the alcohol sulfates are alkali metal salts (such as sodium salts), ammonium salts, or amine salts (such as triethanolamine salts) of butyl sulfates, and alkali metal salts (such as sodium salts) of heptyl sulfate. , Ammonium or amine salt (such as triethanolamine salt), alkali metal salt of octyl sulfate (such as sodium salt), ammonium or amine salt (such as triethanolamine salt), alkali metal salt of decyl sulfate (such as sodium Salt), ammonium or amine salt (such as triethanolamine salt), alkali metal salt (such as sodium salt), ammonium or amine salt (such as triethanolamine salt), alkali metal salt of myristyl sulfate (Such as sodium salt), money or amine salt (such as triethanolamine salt), alkali metal salt (such as sodium salt), ammonium or amine salt (such as triethanolamine salt) of the sulfate ester of lauryl diethylene glycol ether Alkali metal salts (such as sodium salts), ammonium salts, or amine salts (such as triethanolamine salts) of sulfate esters of phenol polyglycol ethers. Alkali metal salts of alcoholic sulfates with 10 to 28 carbon atoms, such as sulphur of lauryl polyethylene glycol ether, can be used. This paper is sized for China National Standard (CNS) A4 (210X297 mm) I- ------ -— ^ ϋ ϋϋ · 1Μ1ϋ mm mu, 1 ml im In nn mi m ml ml ml ϋϋ am—τ— —i · ^ — 1 ^ 11. (Please read the precautions on the back before filling (This page)-21-487697 Employees' cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs, A7, B7 V. Description of the invention (19) Sodium salts of acid salts 6 Excellent compounds are sodium, potassium, lithium, and ammonium benzenesulfonic acid Salt or triethanolamine salt, sodium, potassium, lithium, ammonium or triethanolamine salt of toluenesulfonic acid, sodium, potassium, lithium, ammonium or triethanolamine salt of vinylsulfonic acid, or the like Polymers of vinyl sulfonates, sodium, potassium, lithium, ammonium or triethanolamine salts of lauryl sulfate, sodium, potassium, lithium, ammonium or triethanolamine salts of sulfonic acid Water-soluble formaldehyde condensate, sodium, potassium or lithium salt of cinnamic acid, sodium, potassium or lithium salt of salicylic acid, two of tetrahydrophthalic acid Sodium salt, dipotassium salt or dilithium salt, disodium salt, dipotassium salt or dilithium salt of phthalic acid, toluene expansion acid, benzenesulfonic acid and the like. The use of these compounds as refining agents improves the thermal stability and melt transparency of the products collected in subsequent steps. The best is the aromatic sulfonic acid and its alkali metal salt, because it does not remain in the product collected in the subsequent steps, and it is not easy to cause adverse effects on the quality of the product due to the refined preparation. In step (C), washing the paddle liquid can cause alkali metal halides, residual catalysts, residual alkali metal hydroxides, and other impurities in the paddle liquid to be transferred from the slurry to the water layer in contact with the paddle liquid to obtain a refined liquid. . In addition to these mobile components, the aqueous layer contains a small amount of epihalohydrin and 2,3-epoxypropyl derivative or 2-methylepihalohydrin and 2-methyl-one, originally contained in the slurry in a dissolved state. 2,3-Epoxypropyl derivative. Therefore, in the refining, from the standpoint of product yield, using the smallest amount of water and completing the cleaning action in the shortest time is conducive to improving production efficiency. When the slurry is cleaned with an aqueous solution of the above compound as a fine preparation, satisfactory refining can be performed with a relatively small amount of water in a short period of time. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) > ------ Order --- (Please read the precautions on the back before filling out this page) -22-487697 A7 1 ___ B7_ V. Description of the invention (2〇) The refined liquid does not need to The water layer was transferred to the organic layer, and more particularly, the product collected in the subsequent step (D) was surprisingly found to have a kaolin turbidity of almost 1 upon melting. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) This slurry is better to clean several times than once. Although the effect of refined preparations and its dosage increase, once the dosage exceeds 5wt%, its effect and dosage will not increase in proportion. When the slurry is repeatedly washed as described above, the aqueous solution contains from 0.1 to 5 parts by weight, from 0.05 to 2 parts by weight, per 100 parts by weight of the derivative contained in the slurry. Preferably, from 0.1 to 1 part by weight of the best refined preparation is used for the first and second cleaning, and the amount of the refined preparation in the aqueous solution used for the third cleaning is reduced to 100 parts by weight, the slurry The derivative of the compound is preferably from 0.001 to 5 parts by weight, preferably from 0.001 to 2 parts by weight, and most preferably from 0.001 to 1 part by weight, to avoid contamination of the formed product with the refined preparation. The amount of water used to clean the slurry is 0,5-50 times the weight of 2,3-epoxypropyl derivative or 2-methyl-2,3-epoxypropyl derivative present in the slurry. , 1 to 5 times particularly good. When washing with an aqueous solution of a fine preparation having a relatively low solubility in water, the slurry is preferably washed with a small amount of pure water afterwards. Weak acid neutralizers such as sodium dihydrogen phosphate can coexist in the aqueous solution used for cleaning. The temperature of the aqueous solution used for cleaning is preferably from 10 to 40 ° C, and more preferably from 20 to 30 ° C. The cleaning is performed by contacting the slurry with the aqueous solution in batches or continuously using various known devices. For example, the cleaning action may introduce the slurry with the above-mentioned refined preparations and water separately or simultaneously as an aqueous solution into a container equipped with a stirrer, and the paddle liquid layer and the cleaning water layer are brought into contact with the good paper size by stirring. Applicable to China National Standard (CNS) A4 specification (2 丨 〇 < 297 mm) 487697 A7 B7 V. Description of invention (21) Good. The stirring time depends on the intensity of the stirring, but the stirring usually lasts for a short time of about 5 to 10 minutes. After stirring, the liquid in the container was allowed to stand still. The rest time depends on the intensity of the agitation described above, but it is preferably 5 to 60 minutes, and preferably 10 to 30 minutes in a general stirring example. However, washing the slurry layer with an aqueous solution by stirring in a container may cause an organic layer that is still cloudy, as in the case of insufficient refined agents used in the aqueous solution. It has been found that making fine droplets of the organic layer to ensure that the slurry layer and the cleaning aqueous solution layer are fully in contact, it is quite easy to integrate and form an organic layer again, but the fine droplets of the aqueous solution are not easy to integrate, so it will remain dispersed for a long time to form the organic layer This organic layer was made cloudy. It has also been found that the re-formed water layer does not contain such a large number of fine droplets of the organic layer, but when the organic layer in which the fine droplets of the aqueous solution are dispersed is collected, after the epihalohydrin is evaporated from the organic layer in the subsequent step (D), This organic layer produces a low purity product. It is believed that the movement of a specific impurity from the organic layer to the surface of the droplet allows the droplet to be stably dispersed in the organic layer. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page). It has been found that the high-purity product can be efficiently produced by better cleaning the slurry method, which includes an average diameter of 0 · 1 The aqueous solution droplets up to 10 legs are introduced into the column of the slurry layer, and the droplets are raised in the slurry layer to contact the slurry, and then the aqueous solution layer is integrated or combined with the previously formed aqueous solution layer, and the slurry layer is separated from the slurry layer. Aqueous layer. The liquid droplet cleaning method is preferably applied to a liquid product. The liquid product is obtained by gently stirring the slurry containing the precipitated alkali metal alkali compound prepared in step (B) and a sufficient amount of water or the aqueous solution to dissolve the precipitated alkali. Metal halide (the amount of water or aqueous solution is several times better than the slurry), and the paper size in the paddle liquid obtained in the removal step (B) applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -24-487697 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (22) Alkali metal halide, or by filtering the slurry containing precipitated alkali metal halide. The preferred cleaning method using liquid droplets can produce a clear and refined liquid, and liquid droplets with an average diameter of 0.1 to 10 legs can still be introduced again into the aqueous solution layer previously formed by the upper part of the column to make the liquid droplets rise again. Then combine repeatedly to improve its efficiency. Therefore, step (C) is preferably carried out by a method (C /) for removing a liquid product obtained by precipitating an alkali metal halide. The method (c >) includes setting the average particle diameter to 0.1 to 10 legs (to 0 · 3 to 10 legs are preferred) The aqueous solution droplets containing the refined preparation are introduced into the column of the liquid product layer, so that the droplets rise, and then combine in the column to form an aqueous solution layer. The cycle in the column is gradually repeated. The droplets are introduced, raised, and combined, and the aqueous solution is continuously supplied to the liquid product by the introduction effect, until the amount is 0.01 to 5 parts by weight relative to 100 parts by weight of the derivative in the liquid product. Until the formulation is introduced into the liquid product, a refined liquid is thus formed. The amount of water supplied with the refined preparation in the method (C /) is preferably 50 to 5000 parts by weight relative to 100 parts by weight of the derivative, and the method (C /) can be repeated. The method (C /) The high refining effect makes it possible to achieve effective refining even if it is used in a liquid product containing a large amount of impurities prepared by the better method (B /) of step (B). In addition, even if the amount of the refined preparation is reduced, the method (C >) can be effectively purified without leaving the aqueous solution in the organic layer. An extreme example is proposed. The cleaning method (C >) using water containing no refining agent can still improve the refining effect in a short time, in which the organic layer and water are stirred in a container, and then left for a long time. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) · — ^ — (Please read the notes on the back before filling this page)

1T -25-487697 A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Collect the organic layer after the description of the invention (23). In particular, because in the manufacture of crystalline derivatives' such as tris (2,3-epoxypropyl) isocyanurate or tris (2-methyl-2,3-epoxypropyl) ester or terephthalic acid In the case of bis (2,3-epoxypropyl) ester or bis (2-methyl-2,3-epoxypropyl) ester, the purity can be further improved in the subsequent refining step (E). The method (C /) of the water of the preparation, that is, the method (C ") is suitable for producing these crystalline derivative products, the method (C〃) includes the average diameter of 0 · 1 to 10 mm (with 0 · 3 to 1 0 mm is preferred) Water droplets containing no refined preparation are introduced into a column for removing a liquid product layer prepared by precipitating an alkali metal alkali compound, so that the droplets rise in the liquid product layer, and then an aqueous layer is formed in the column. The liquid layer was again introduced above the column with droplets having an average diameter of 0.1 to 10 mm (preferably from 0.3 to 10 brains), and then it was also raised and combined, and repeated introduction, ascent and combination of droplets Composition cycle, and continuously introduce water into the liquid product until the amount of water relative to 100 parts by weight of the derivative in the liquid product 50 up to 5,000 parts by weight. Repeatable method (C〃). The apparatus designed for these methods can be used to repeatedly introduce, raise, and combine with an aqueous solution layer an aqueous solution droplet having an average diameter of 0.1 to 10 legs. For example, the device includes a main cylinder, a cylindrical reservoir connected to the upper end of the main cylinder, and another cylindrical reservoir connected to the lower end of the main cylinder, a cover covering the upper reservoir, and via the cover. The axis of rotation extends from the center to the lower end of the main cylinder. The inner diameter of the upper reservoir is almost the same as that of the main cylinder, it is high enough to store liquid, and it has a discharge hole above. The cover is provided with a liquid supply extending to the lower end of the upper reservoir. The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page) 487697 A7 1 __B7__ 5 , Invention description (24) tube. The inner diameter of the lower reservoir is almost the same as that of the main cylinder, it is deep enough to hold liquid, and it has a drain hole at the bottom. In the middle of the lower reservoir, there is a liquid supply pipe extending sideways to near the lower end of the rotating shaft. A plurality of discs having a plurality of holes are arranged around the rotating shaft at a fixed distance from the lower end of the shaft to the upper end of the main cylinder. An annular baffle is interposed between the discs on the inner wall of the main cylinder. The hoop is mounted below the periphery of each disc. The holes in each disc are open, passing through the upper surface to the lower surface so that droplets with an average diameter of 0.1 to 10 legs pass through the hole. When the rotary shaft is connected to the upper drive system and driven, the rotary shaft rotates alternately at a specific rotation angle. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Organic fluids that are not miscible and have a higher specific gravity than water enter the cleaning device through the supply duct connected to the cap until the upper reservoir is half full. When the rotating shaft rotates alternately, the aqueous solution for cleaning is supplied to a supply pipe extending from a reservoir below. The aqueous solution is released in the organic fluid through the outlet of the supply pipe, and is blocked by a ring fixed to the lowermost disk, and droplets are formed in the organic fluid through the hole. The droplets are released upstream of the organic fluid column above the disc and are dispersed in the organic fluid as they rise. The baffle slurry dispersed droplets fixed on the inner wall of the main disc are guided to the center of the main cylinder, so that the droplets can be blocked and combined in a ring fixed on the second disc at the bottom to form the solution layer. After that, through the hole of the second disc at the bottom, the aqueous solution is released again as a droplet upstream of the organic fluid, and then when it rises, the droplet is dispersed in the organic fluid column. In this way, when the aqueous solution is dispersed into droplets, the aqueous solution supplied from the middle of the lower reservoir rises, and the droplets form a bond when they reach the surface of the organic fluid column in the upper reservoir. The Chinese national standard (CNS) A4 is applied to this paper scale. Specifications (210X297 mm) -27-487697 A7 B7 Approved by the central h Employee Consumption Cooperative V. Description of Invention (25) This forms a solution layer on the organic fluid column and stores it. 0 Amount of aqueous solution stored above the organic fluid column Increasing with additional continuous supply of the aqueous solution> When the aqueous solution reaches the upper reservoir discharge hole, the aqueous solution overflows and is discharged from the drainage hole. Continuous supply of organic fluid and the aqueous solution layer causes the organic fluid and the aqueous solution to continuously contact in countercurrent. The feed rate of the organic fluid and the aqueous solution can be adjusted to 3 m, and the droplet size of the aqueous solution can be changed by changing the rotation speed of the rotation axis. In order to adjust 〇 such cleaning devices are commercially available, the liquid product and the aqueous solution are continuously supplied to the cleaning device so that the liquid products and the aqueous solution can be continuously contacted in the cleaning device and the bottom of the cleaning device is continuously collected refined liquid. In these cleaning methods, it is also preferable to continuously supply an aqueous solution of the refined preparation until 0 to 0 1 to 5 parts by weight of the refined preparation per 100 parts by weight of the organic fluid. These cleaning devices are also suitable for the method (C) > It uses water containing no refining agent. In this way, a refined liquid containing epihalohydrin is prepared in step (C). For example, epichlorohydrin is white to 70 to 90 W t%. In step (D), evaporation is performed. Action to remove epihalohydrin or 2-methyl epihalohydrin and a small amount of other volatile combinations in the resulting refined liquid to form a group containing no such volatile groups The product 0 leads the vapor to a condenser and is collected in a liquid form. The epihalohydrin or 2-methylepihalohydrin can be evaporated using, for example, a common distillation column, a rotary evaporator flash evaporator, or a falling film evaporator. The refined liquid was concentrated. However, when the epihalohydrin or 2-methyl epihalohydrin concentration was close to 10 W t%, the liquid Uti. Became extremely viscous 0. In particular, when the liquid WsjL was epihalohydrin or 2-methyl When the epihalohydrin concentration is lower than 1 W t%, these volatile groups are written on this page. The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm). Please read the precautions on the back first. 28-487697 A7 * B7 V. Description of the Invention The evaporation rate of the (26) component suddenly drops, so it is difficult to effectively remove these volatile components. It has been found that the improperly refined liquid obtained in step (c) is at a high temperature of 100 to 165 ° C, and the concentration of these volatile components is less than 10 W t%, especially less than 1 wt%. The alkoxy content decreases. The decrease in the ethylene oxide oxygen content is considered to be caused by trace residual impurities caused by insufficient cleaning in step (C). However, when an insufficient amount of an aqueous solution is used, the increase in the number of washings in step (C) does not help to completely remove impurities, and it unduly reduces the yield of the product obtained in step (D). Therefore, it is better to use an aqueous solution of a refined preparation having a high refining effect for the refining of the step (C), so as to obtain a refined liquid containing a tolerable amount of impurities. The liquid removes these volatile components to obtain a product substantially free of these volatile components. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) It has been found that the substrate heated to a temperature of 100 to 16 5 ° C contains a concentration of 1 to 6 Ow t % Is a suitable refined liquid of epihalohydrin or 2-methyl epihalohydrin or its concentration solution, so that these volatile components can be quickly evaporated from the film and the concentration of volatile components in the film can be reduced. 5 0 0 // m thin fluid film. However, it is impossible to actually make a thinner film than 30 / zm from the purified liquid or its concentrated liquid, because the surface area of the film formed from the purified liquid or its concentrated liquid per unit weight is also relatively increased. According to a preferred embodiment of the present invention, a coater is used to form a 30 to 5 0 0 // m thick layer made of a refined liquid or a concentrated liquid on a substrate heated to a temperature of 100 to 16 ° C. The film is preferably 100 to 450 // m, and under reduced pressure, the pressure of the volatile component is preferably at most 5 legs H g. The volatile component is evaporated from the film, which can be reduced in a short time. The concentration of volatile components in the film. This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm)-29-487697 A7 B7 V. Description of the invention (27) The concentration of volatile components in the fluid film can be continuously heated by the film or by A more efficient method is to evaporate the volatile components, reducing it to a level where the film is substantially free of these volatile components, in other words less than 100 P pm (by weight). According to a more specific embodiment of the present invention, the volatile components in the refined fluid or its concentrated liquid can be effectively removed by the method (D /). The method (D /) includes coating a refined liquid or a concentrated solution on a substrate surface. Liquid film with a thickness of 30 to 500 / zm, preferably 100 to 450 // m, 'make the concentration of the volatile component in the refined liquid at one end of the film or its concentrated liquid the highest' and gradually reduce the concentration until the other end of the film The concentration is the lowest, and under the pressure of 5 mm H g or less (for example, from 0.1 to 5 fflffl η g) at 100 to 165 ° C, preferably at 120 to 160 ° C, the volatility is evaporated from the film At the same time, the refined liquid or its concentrated liquid is continuously supplied to the highest end of the volatile component concentration of the film. After evaporation and the thickness of the film decreases, it is gradually transported toward the other end of the liquid and continuously from the other end of the film. The final liquid with reduced volatile component concentration is recovered. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). According to the method (D /), epihalohydrin in the refined liquid prepared in step (C) can be used in a short time- 2-Methylepihalohydrin and other volatile components are removed to a level that is substantially free of volatile components, so the formation of insoluble materials that may occur when high-temperature removal of these volatile components is significantly suppressed. Therefore, the method (D ~) can be used in the methods (B) and (C) without using the better method (B /), the better method (C >), and the better method (C ") (wherein no refined preparation is used) The resulting refined liquid containing a large amount of impurities produces a product containing no insoluble matter. Especially for the production of crystalline derivatives, the size of this paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -30-487697 A7 B7 V. Description of the invention (28) Examples of materials' Three isocyanurates (2, 3 -Glycidyl ester or tris (2-methyl-2,3-glycidyl) ester, or bis (2,3-glycidyl) phthalate or bis (2-methyl -2,3-epoxypropyl ester), the above-mentioned insoluble matter in the product obtained in step (D) cannot be removed in the subsequent refining step (E). However, if the product obtained in step (0) does not contain insoluble matter, the purification step (E) can achieve higher purity. Therefore, the method (D >) is more suitable for the manufacture of these crystalline derivative products. It is printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs.-(Please read the precautions on the back before filling this page) d Use this The evaporator designed by the method can smoothly perform the better method of removing volatile substances. For example, the evaporator includes a cylinder which is covered by a cap having a liquid inlet and a vapor outlet, and a liquid outlet at the bottom. A sleeve is provided around the cylinder to circulate the heat medium, and the cylinder is connected to a vacuum pump equipped with a condenser through a steam outlet. Inside the cylinder is really a rotating shaft agitated by the cover, a disk fixed above the shaft, and an applicator under the disk, the applicator is fixed to the end of a frame fixed to the shaft via a spring, Or it is supported by a frame fixed to the end of the rod extending from the shaft. The applicator is pressed against the inner wall of the cylinder with a spring-controlled force or centrifugal force during rotation, so that it slides along the inner wall of the cylinder when the rotation axis rotates. The shape of the applicator is a rectangular parallel tube and has a long plate surface facing the cylinder. The surface is cut into a plurality of grooves at a certain distance from top to bottom, so that the surface is staggered with the vertical plane at an angle. The thickness of the film formed on the inner wall of the cylinder can be adjusted by adjusting the strength of the spring pressing the applicator against the inner wall of the evaporator, the feed rate of the refined liquid and its concentrated liquid, the temperature of the film in the evaporator, and the like. The refined liquid or its concentrated liquid passes through the liquid in the cover. The paper size applies the Chinese National Standard (CNS) A4 specification (21 OX297 mm) -31-487697 A7 __ B7 V. Description of the invention (29) The inlet is supplied to the cylinder. Inside the disc, the centrifugal force when the shaft rotates flows on the disc toward its circumference, and reaches the top of the inner wall of the cylinder after passing through the circumference of the disc. The applicator panel surface is distributed on the inner wall of the cylinder, and a film is formed on the inner surface of the cylinder. When the refined liquid or its concentrated liquid is continuously supplied, when the applicator is driven down the inside of the cylinder through an inclined groove, the refined liquid or concentrated liquid and the film facing the edge of the surface of the cylinder's applicator panel mixing. Therefore, a refined liquid or a concentrated liquid is continuously supplied, and a film is formed on the entire inner wall of the cylinder when the rotary shaft is rotated. When the volatile component is evaporated from the refined liquid or its concentrated liquid, the refined liquid or its concentrated liquid is continuously supplied on a rotating shaft. As a result, when the applicator passed through the film at the same time, the concentration of the volatile components in the film decreased downward, so that the top concentration of the inner wall of the cylinder was the highest and the bottom concentration was the lowest. In addition, when the refined liquid or its concentrated liquid is continuously supplied by the rotation of the rotating shaft, the film portion with the lowest concentration of volatile components accumulates at the bottom of the evaporator and is the final liquid. The accumulated liquid is recovered through an outlet at the bottom of the evaporator. Evaporators performing this evaporation are known and commercially available. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Use the evaporator to remove the volatile components from the refined liquid or its concentration, and gradually reduce the concentration of the volatile components. First reduce to 2 0 0-4 0 0 0 p pm, then lower to the level of volatile components in the formed refined liquid, and reduce the concentration to 1 000 p prn or less (specially) It is better to reduce it to 50 p pm or below). When the product is purified by recrystallization described below, it is not necessary to remove the volatile components by evaporation to a level where the product is substantially free of volatile components, and the product may contain a table of about 100 p ppm Halohydrin or 2-methylepidentate. This paper size is in accordance with Chinese National Standard (CNS) A4 specification (21 × 297 mm) 487697 A7 B7 V. Description of the invention (30) Better derivatives such as phthalic acid and isophthalic acid can be prepared from step (D) Bis (2,3-epoxypropyl) or bis (2-methyl-2,3-epoxypropyl) esters of acid or terephthalic acid; trimellitic acid or trimesic acid three (2, 3 mono-glycidyl ester or bis (2-methyl-2,3-glycidyl) ester of hydantoin, N, N-bis (2,3-glycidyl) derivative or N, N —bis (2-methyl-2,3-epoxypropyl) derivative; and tris (2,3-epoxypropyl) isocyanatoate or tris (2-methyl-2) , 3-epoxypropyl) ester, which is a purified product. As described above, in steps (A) to (D), a preferred method can be used separately, and the preferred methods (A) to (D) can be used in combination to obtain a high-purity epoxy compound. A preferred method is a method including step (A), step (B) performed by method (B >), step (C) performed by method (C /), and step (D); including step (A), Method (B), step (C) performed by method (B /), and method (D) performed by method (D >); including step (A), step (B), and method (C / ) Step (C) and the method (D > printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page)) and so on. The best method includes step (a) and method (B <) Step (B) performed, step (C) performed by method ((: /), and step (d) performed by method (D /). These preferred methods and best methods are suitable for large scale Industrial production. In particular, in the production of crystalline derivatives, such as bis (2,3-epoxypropyl) ester of phthalic acid or bis (2-methyl-2,3-epoxypropyl) ester, isopropyl The tris (2,3-epoxypropyl) ester or tris (2-methyl-2,3-epoxypropyl) cyanurate can be a better method without the use of refined preparations (^ Paper size applies China National Standard (CNS) A4 Specification (21〇 > < 297 mm) " 487697 A7 B7 V. Description of the Invention (31) C ") and a combination of these preferred methods to produce high purity products of these derivatives. These combined examples are methods using method (B >) and method (D >) and step (B) and step (〇) after step (A), and using methods in step (B) and step (C) (B >) and the method (C 不) without using the refined preparation, and the method (C〃) and the method (D /) without using the refined preparation, respectively, in step (C) and step (D) The best method is the method of step (B), step (C) and step (D) respectively using the method (B /), the method without using a refined preparation (C〃), and the method (D >). Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Among the derivatives that can be obtained in step (D), crystalline compounds such as bis (2,3-epoxyphthalic acid) Propyl) ester, tris (2,3-epoxypropyl) isocyanurate and tris (2-methyl-2,3-epoxypropyl) isocyanurate can be used in step (D ) And further purified by recrystallization in step (E). In step (E), in order to dissolve the product recovered in step (D), methanol, ethanol, propanol, methyl ethyl ketone, ethyl acetate, benzene, toluene, or a mixture thereof may be used as a solvent, and methanol is particularly preferred. For recrystallization, the product is dissolved in a solvent at 1 to 10 times the weight of the product at about the boiling point of the solvent, preferably 2 to 6 times, and a cooling rate of 2 to 30 t / hour. It is better to cool gradually to form a solution, until crystals precipitate. The precipitated crystals are separated from the solution by a general method such as filtration, and the separated crystals are washed with the same solvent as necessary, and then dried by a general method to recover the final product. Compared with the product before purification by recrystallization, this final product has low epoxy equivalent and high thermal stability. Step (E) is applicable to large-scale industrial production, especially large-scale industrial paper sizes of high-purity final products. Applicable to China National Standard (CNS) A4 specification (210X297 mm) Fine -34-487697 A7 B7 Central Bureau of Standards, Ministry of Economic Affairs Printed by the employee consumer cooperative V. Invention description (32) Industry production, and it is performed after step (D) regardless of the method of use (B >), method (C /), method (CC), or method (D /) . Example 1 Step (A) •• A 2 glass reaction flask equipped with a paddle stirrer was charged with 20 g of water, 5.5 g of tetraethylammonium bromide, 925 g (10 mo 芡) of epichlorohydrin, and i66 g (lmoj ?) Terephthalic acid to form a reaction mixture. The reaction mixture in the flask was then heated with stirring to raise its temperature. When the temperature of the reaction mixture reached 89 ° C, the reaction mixture began to boil at atmospheric pressure. The heating effect continued for 3 hours, and the evaporation generated by the cooling of the condenser continued to return the liquefied epichlorohydrin to the flask, and the liquefied water was discharged from the flask. When the temperature of the reaction mixture reached 121 ° C, the heating was stopped, and the reaction mixture was cooled at 45 ° C to obtain a reaction product. Analysis by liquid chromatography confirmed that the reaction product did not contain a carboxyl group due to the raw material phthalic acid. Step (B): Then, 176 g (indicated as Namo Η 为 2.2mo $) of 50 wt% sodium hydroxide was added dropwise to the entire reaction mixture maintained at 45 ° C in a flask, which was Starting at 100 leg Hg under reduced pressure, a reaction mixture was formed, while water and epichlorohydrin were evaporated from the reaction mixture under vigorous stirring. Gradually increase the vacuum while cooling it with a condenser, return all liquefied epichlorohydrin to the flask continuously, and drain the liquefied water out of the flask. When the degree of vacuum reaches 60 legs Hg ', the dropwise addition is terminated, and a solution containing precipitated sodium chloride is prepared. The dropwise addition takes 6 hours. During the addition, the reaction under stirring due to the precipitation of sodium chloride (please read the precautions on the back before filling this page), and then fill in the items. The size of the paper for the binding and binding is applicable to the Chinese National Standard (CNS) A4 specification ( 210X297 mm) -35-487697 A7 B7 V. Description of the invention (33) The mixture becomes cloudy, but the whole is maintained uniform. According to liquid chromatography analysis, the prepared slurry contained less than 1 wt% of a compound having a 2-carboxyl-3-chloropropyl group. Step (C): The whole slurry prepared in step (B), 600 g of distilled water, and 2 g of sodium toluenesulfonate were stirred in a glass container for 5 minutes, and then left for 10 minutes. The entire first epichlorohydrin layer was recovered, and the water layer was transferred to another container. The whole epichlorohydrin layer, 600 g of a 5 wt% sodium dihydrogen phosphate solution in distilled water and 2 g of sodium tosylate were stirred in a glass bottle for 5 minutes, and left to stand for 10 minutes. Recover all the second epichlorohydrin layer and move the water layer to another container. Then, the whole recovered second epichlorohydrin layer and 800 g of distilled water were stirred in a glass container for 5 minutes, and allowed to stand for 10 minutes. The entire epichlorohydrin layer was recovered as a refined liquid. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Step (D): Introduce all the final epichlorohydrin layers obtained in step (C) into a rotary evaporator and decompress it Epichlorohydrin is removed by heating. Before evaporation stops, heat at 140 ° C for 1 hour under a reduced pressure of 2 mm Hg. It was cooled to room temperature and the inner container in the evaporator was recovered to obtain 257 g of the product. Based on the raw material terephthalic acid used in step (A), the number of products calculated was equivalent to a 92% yield. Ionic chloride was not measured in this product. The epoxy equivalent of this product was 146, the kaolin turbidity was 1 or less when melted at 140 ° C, and it was heated in a sealed container at 150 ° C for 2 4 hours The rear epoxy equivalent is 148. The calculation found that the change in epoxy equivalent when heated was 1.4%. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X297 mm) '-36-487697 A7' B7 V. Description of the invention (34) Step (E): The product obtained in the melting step (D), in Under stirring in the flask, 100 g of the melt was gradually added to 400 g of methanol to form a solution of the product in methanol. The solution was heated to the reflux temperature of methanol and then cooled to 5 ° C within 12 hours. White crystals precipitated in the solution. White crystals were separated by filtration and then dried to obtain 7 5 g of the final product. The epoxy equivalent of the final product is 140, the turbidity of kaolin melted at 140 ° C is 1 or less, and the epoxy equivalent after heating at 150 ° C for 24 hours in a closed container is 1 4 1. The epoxy equivalent caused by heating changed to 0.7%. 〆, Comparative Example 1 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Stir the slurry prepared in the same way as in step (B) of Example 1 and make it the same as in the example. Step 1 (C) was left in the same manner, but sodium tosylate was not used. Even after being left for 10 minutes, the epichlorohydrin layer was severely cloudy. It was left for another 12 hours, and the epichlorohydrin layer was recovered as the first epichlorohydrin layer. The second washing was performed in the same manner, but without using sodium toluenesulfonate. After 10 minutes, the epichlorohydrin layer was still severely cloudy. This epichlorohydrin layer was recovered after being left for 12 hours, and was the second epichlorohydrin layer. The final washing was performed in the same manner, but without using sodium tosylate, the epichlorohydrin layer was still severely cloudy after 10 minutes of standing. After being left for 12 hours, it was recovered as the final epichlorohydrin layer. The final epichlorohydrin layer was treated in the same manner as in step (D) of Example 1, and 251 g of the product was recovered from the evaporator. This product has an epoxy equivalent of 151 and an ion chloride content of 5 wt. PPm. When melting at 140 ° C, the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm 1 487697. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. A7 * ____B7_ V. Description of the invention (35) Kaolin has a turbidity of 2, and the epoxy equivalent is 1 58 after heating at 150 ° C for 24 hours. The calculation shows that the epoxy equivalent changes to 4. · 6%. The product was treated in the same manner as in step (E) to obtain 70 g of a dry final product in the form of white crystals. The epoxy equivalent of the final product was 142, and the turbidity of kaolin melted at 140 ° C was 2 in a sealed container. The epoxy equivalent at 2 ° C for 1 hour at 150 ° C is 145. The calculation found that the epoxy equivalent changed to 2%. Example 2 Steps (A) and (B): Take step 1 of Example 1 (A ) A slurry containing precipitated sodium chloride was prepared in the same manner as in (B). Step (C): The final epichlorohydrin layer was recovered in the same manner as in step (C) of Example 1, but using 2 g of sodium vinylsulfonate Instead of 2 g of sodium tosylate. Step (D): treated in the same manner as in step (D) of Example 1. The entire final epichlorohydrin layer prepared in step (C) was recovered from the evaporator as 257 g of product. Ionic chlorine was not measured in the product, and the epoxy equivalent of the product was 1 4 6 at 1 4 0 Kaolin clay turbidity is 1 or below when melting at ° C, and the epoxy equivalent weight after heating at 150 ° C for 24 hours in a closed container is 14 8. Example 3 Steps (A) and (B) ·· To implement Example 1 steps (A) and (B) in the same way to prepare a slurry containing precipitated sodium chloride. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) " -38-. Please read the notes on the back before filling this page) Order 487697 A7 B7 V. Description of the invention (36) Step (C): Recover the final epichlorohydrin layer in the same way as in step (C) of Example 1 but use 2 g Xinyuan sodium dextrose replaces 2 g of sodium tosylate. Step (D): The entire final epichlorohydrin layer prepared in step (C) is treated in the same manner as in step (D) of Example 1, and is therefore recovered from the evaporator 2 5 7 g of product. No ionic chlorine was measured in this product. The epoxy equivalent of this product was the same as that obtained in Example 1. It melted at 140 ° C. When the kaolin has the same turbidity, the epoxy equivalent is the same after heating at 150 ° C for 24 hours in a closed container. Example 4 Steps (A) and (B): Steps (A) and (B) of Example 1 ) To prepare a slurry containing precipitated sodium chloride. Step (C): The final epichlorohydrin layer was recovered in the same manner as in step (C) of Example 1, but 2 g of ammonium tosylate was used instead of 2 g of tosylate. Sodium. Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Step (D): The entire final table prepared in the same way as in step (D) of Example 1 and processed in step (C) The chlorohydrin layer was therefore recovered from this evaporator at 2 5 6 g. Ionic chloride was not measured in this product. The epoxy equivalent of this product was 147, and the kaolin turbidity was 1 or less when melted at 14 ° C, and 150 ° C in a closed container. (: The epoxy equivalent after heating for 24 hours is 150. Calculation shows that the change in epoxy equivalent is 2%. Example 5 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm)-39- 487697 A7 ______B7 V. Description of the invention (37) Steps (A) and (B): Repeat step (A) of Example 1, but replace the table of 9 2 5 g with 10 6 5 g of 2-methylepichlorohydrin Chlorohydrin. When the temperature of the reaction mixture reaches 95 ° C, 2-methylepichlorohydrin begins to reflux. The reaction mixture is finally heated to 120 ° C within 8 hours. 176 g of 50 wt% hydrogen An aqueous solution of sodium oxide was added to the reaction mixture, and the temperature was maintained at 45 ° C. for 6 hours by the method in step (B) of Example 1. A slurry containing precipitated sodium chloride was prepared. Step (C): The step (C) of Example 1 was used. ) Was recovered in the same manner, but 2 g of potassium benzenesulfonate was used in place of 2 g of sodium tosylate, and the final 2-methylepichlorohydrin layer was recovered. Step (D): The procedure of Example 1 ( D) Treat the entire final 2-methylepichlorohydrin layer obtained in step (C) in the same manner, so 284 g of product is recovered from the evaporator. Ionic chlorine was not measured in this product. The epoxy equivalent of this product was 16 3, and the kaolin turbidity was 1 or less when melted at 140 ° C. After heating at 150 ° C for 2 4 hours in a closed container The epoxy equivalent is 16 5. The calculation found that the epoxy equivalent changed to 1.2%. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (Please read the precautions on the back before filling this page) Example 6 Step (A ): A 2 j? Glass reaction flask equipped with a paddle stirrer was charged with 30 g of water, 5.5 g of tetramethylammonium chloride, 1.388 g (15 moj?) Of epichlorohydrin, and 129 g (1 m 〇p) Cyanuric acid forms a reaction mixture. The reaction mixture in the flask is then heated with stirring to raise its temperature. When the temperature of the reaction mixture reaches 8 9 ° C, the reaction mixture begins to boil under atmospheric pressure. Applicable to Chinese National Standard (CNS) A4 specification (21GX297mm) -40-487697 Printed by A7-B7 of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (38) The heat action lasts for 5 hours and is generated by condenser cooling Evaporate and continuously liquefy epichlorohydrin Return to the flask and drain the liquefied water out of the flask. When the temperature of the reaction mixture reaches 120 ° C, stop heating and cool the reaction mixture at 45 ° C to obtain a reaction product. The reaction was obtained with cyanuric acid. Step (B) •• Then, 2 5 6 g (indicated by Na 2 O 3 as 3 · 2moj?) Of 50 wt% sodium hydroxide was added dropwise to the flask to maintain 50 ° In the entire reaction mixture of C, it was started at a reduced pressure of 100 μg Hg, and a reaction mixture was formed, while water and epichlorohydrin were evaporated from the reaction mixture under vigorous stirring. Gradually increase the degree of vacuum while cooling it with a condenser, and return all the liquefied epichlorohydrin back to the flask 'to drain the liquefied water out of the flask. When the degree of vacuum reaches 60 legs H g, the dropwise addition is ended to prepare a solution containing precipitated sodium chloride. The dropwise addition takes 6 hours. During the addition, the reaction mixture became cloudy with stirring due to the precipitation of sodium chloride, but the whole was kept uniform. According to liquid chromatography analysis, the prepared slurry contained less than 1 wt% of a compound having 2 -carboxyl-3 -chloropropyl. Step (C): The whole slurry prepared in step (B), 600 g of distilled water, and 2 g of sodium tosylate were stirred for 5 minutes' in a glass container, and then left for 10 minutes. The entire first epichlorohydrin layer 'was recovered and the water layer was transferred to another container. Then the whole recovered epichlorohydrin layer '600 g 5 w t% sodium dihydrogen phosphate solution in distilled ice and 2 g of sodium tosylate were stirred in a glass bottle for 5 minutes, and left to stand for 10 minutes. Recycle all second-layer epichlorohydrin layers' Apply this paper size to Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)% • Items are refilled · Packed · Ordered -41-487697 A7 B7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the Invention (39) The water layer was moved to other containers. Then, the whole recovered second epichlorohydrin layer and 800 g of distilled water were stirred in a glass container for 5 minutes, and allowed to stand for 10 minutes. The entire epichlorohydrin layer was recovered as a refined liquid. Step (D): The entire final epichlorohydrin layer obtained in step (C) is introduced into a rotary evaporator, and the epichlorohydrin is removed by heating under reduced pressure. Before evaporation ceased, heat at 140 ° C for 1 hour under a reduced pressure of 2 ram H g. It was cooled to room temperature and the inner container in the evaporator was recovered to obtain 267 g of product. Based on the raw material cyanuric acid used in step (A), the number of products calculated is equivalent to 90% yield. Ionic chloride was not measured in the product. The epoxy equivalent of the product was 103, the kaolin turbidity was 1 or less when it was melted at 140 ° C, and it was heated in a sealed container at 150 ° C for 2 to 4 hours. The epoxy equivalent is 104. The calculation found that the change in epoxy equivalent when heated was 1%. Step (E): Melt the product obtained in step (D). Under stirring in the flask, 100 g of the melt is gradually added to 400 g of methanol to form a solution of the product in methanol. The solution was heated to the reflux temperature of methanol and then cooled to 5 ° C within 12 hours. White crystals precipitated in the solution. The white crystals were separated by filtration, and then dried to obtain 8 2 g of the final product. The epoxy equivalent of the final product was 99, and the turbidity of the kaolin melted at 140 ° C was 1 or less. After heating at 50 ° C for 24 hours, the epoxy equivalent was 9 9. It was found that the epoxy equivalent caused by heating was changed to 0%. (Please read the precautions on the back before filling in this page) This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -42-487697 Μ * Β7 _____ V. Description of the invention (4〇) Comparative Example 2 Use In the same manner as in step (c) of Example 6, the slurry prepared in the same manner as in step (B) of Example 6 was left, except that sodium toluoate was not used. Even after being left for 10 minutes, the epichlorohydrin layer was severely cloudy. It was left for another 12 hours, and the epichlorohydrin layer was recovered as the first epichlorohydrin layer. The second washing was performed in the same manner, but after leaving without using sodium tosylate 'for 10 minutes, the epichlorohydrin layer was still severely cloudy. This epichlorohydrin layer was recovered after being left for 12 hours, and was the second epichlorohydrin layer. The final cleaning was performed in the same manner, but sodium tosylate was not used. After being left for 10 minutes, the epichlorohydrin layer was still severely cloudy. After remaining for 12 hours, it was recovered as the final epichlorohydrin layer. The final epichlorohydrin layer was treated in the same manner as in step (D) of Example 1, and 258 g of the product was recovered from the evaporator. This product has an epoxy equivalent of 108, an ion chloride content of 4 ppm by weight, a kaolin turbidity of 3 when melted at 1 40 ° C, and an epoxy equivalent of 1 1 3 after heating at 150 ° C for 24 hours. The calculation found that the epoxy equivalent changed to 4.6%. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). The product was treated in the same manner as in step (E) of Example 6 to obtain 80 g of dry final product in the form of white crystal . The epoxy equivalent of the final product was 100, the turbidity of the kaolin melted at 140 ° C was 2, and the epoxy equivalent in the sealed container heated at 150 ° C for 24 hours was 101. Calculations revealed a change in epoxy equivalent of 1%. Example 7

Steps (A) and (B): Steps (A) and (B in Example 6) This paper size applies Chinese National Standard (CNS) A4 specifications (210X2 ^^ -----43-487697 A7 B7 Central Bureau of Standards, Ministry of Economic Affairs Printed by the Staff Consumer Cooperative V. Invention Note (41)) A slurry containing precipitated sodium chloride was prepared in the same manner, but 5 β 5 g of ethyltriphenylphosphonium bromide was used instead of 5 · 5 g of tetramethylammonium chloride. Step (C): The final epichlorohydrin layer is recovered in the same manner as in Step (C) of Example 6. Step (D): The entire final prepared in Step (C) is processed in the same manner as in Step (D) of Example 6. The epichlorohydrin layer, so 265 g of product was recovered from the evaporator. Ionic chlorine was not measured in this product. The epoxy equivalent of this product was 104, and the kaolin turbidity was 1 when melted at 140 ° C. Or below, the epoxy equivalent after heating at 150 ° C for 24 hours in a sealed container is 105. The calculation shows that the epoxy equivalent changes to 1%. Example 8 Steps (A) and (B): A slurry containing precipitated sodium chloride was prepared in the same manner as in steps (A) and (B) of Example 1. Step (C): The final table was recovered in the same manner as in Step (C) of Example 1. Alcohol layer, but using 2 g of toluenesulfonic acid instead of 2 g of sodium tosylate. Step (D): The entire final epichlorohydrin layer prepared in step (C) is treated in the same manner as in step (D) of Example 1, so 2 5 5 g of product was recovered from the evaporator. Ionic chlorine was not measured in the product. The epoxy equivalent of the product was 146. The kaolin turbidity was 1 or less when melted at 140 ° C. In a closed container The epoxy equivalent after heating at 150 ° C for 24 hours is 148. The calculation found that the epoxy equivalent changed to 1.4%. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). ) (Please read the note-item on the back before filling in too: write this page)

1T -44-487697 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7-_____B7 V. Description of Invention (42) Example 9 Steps (A) and (B): Steps (A) and (B) of Example 1 In the same manner, a slurry containing precipitated sodium chloride was prepared. Step (C): The final epichlorohydrin layer was recovered in the same manner as in step (C) of Example 1, but 2 g of sodium benzoate was used instead of 2 g of sodium tosylate. Step (D): The entire final epichlorohydrin layer obtained in step (C) was treated in the same manner as in step (D) of Example 1, so 258 g of product was recovered from the evaporator. Ionic chlorine was not measured in this product. The epoxy equivalent of this product was 1 4 7 and the kaolin turbidity was 1 or less when melted at 1 40 ° C. It was heated at 150 ° C for 2 4 hours in a closed container The subsequent epoxy equivalent is 150. Calculations revealed a change in epoxy equivalent of 2%. Example 10 Steps (A) and (B): A slurry containing crystalline sodium chloride was prepared in the same manner as in steps (A) and (B) of Example 1. Step (C): Return to the final epichlorohydrin layer in the same manner as in step (C) of Example 1, but use 2 g of triethanolamine tosylate and 2 g of sodium tosylate. Step (D): In the same manner as in step (D) of Example 1; the entire final epichlorohydrin layer prepared in step (C), so 256 g of the product was distilled from this. Ionic chloride was not measured in this product. The ring of this product is equivalent to 1 4 7 and the turbidity of kaolin when melted at 1 40 ° C is the ring after heated at 150 ° C for 2 4 hours in a closed container. Oxygen when stomach

I 45-(Please read the notes on the back before filling in, filling-: write this page) Order 487697 A7 B7___ V. Description of the invention (43) 149. The calculation found a change in epoxy equivalent of 1.4%. Example 1 1 Using a reaction vessel equipped with a paddle stirrer at 200 μP, the scale of Example 1 was increased by 10 times. Step (A) proceeds smoothly in the same manner as in Example 1. Step (B) was performed in the same manner as in Example 1, but during the addition of the sodium hydroxide aqueous solution, a part of the precipitated sodium chloride began to accumulate on the side wall near the bottom of the reactor. In addition, when sodium hydroxide aqueous solution is added, more precipitated sodium chloride accumulates and adheres to the side wall of the reactor. Continue to add sodium hydroxide and increase the speed of the stirrer, but the sodium hydroxide on the side wall until the end of the reaction will not be dispersed in the reaction mixture. The resulting slurry contained less than 1 wt% of a compound having 2-hydroxy-3-chloropropyl. Step (C) proceeds smoothly in the same manner as in Example 1. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Step (D) was successfully performed in the same scale and the same way as in Example 1, but the yield was slightly reduced to 90%. The epoxy equivalent of this product is 151, the turbidity of kaolin melted at 140 ° C is 1 or less, and the epoxy equivalent after heating at 150 ° C for 24 hours in a sealed container is 155. The calculation found that the epoxy equivalent change caused by heating was 2.6%. Step (E) was carried out smoothly in the same scale and the same manner as in Example 1, but the yield of the final product formed was reduced to 72%. The epoxy equivalent of the final product was 140, and the epoxy equivalent after heating at 150 ° C for 24 hours in a sealed container was 141. This & Zhang scale applies to Chinese National Standard (CNS) A4 specifications (210 '乂 297 mm) -46-487697 A7 B7 V. Description of the invention (44) Example 1 2 Use two with a length of 15 cm and a width of 2 A reactor with cm and a thick 2 臓 baffle was used instead of Example 11. Step (A) proceeds smoothly in the same manner as in Example 11. In step (B), the reaction mixture is kept homogeneous by stirring, unlike in Example 11, it does not cause precipitation of sodium chloride to accumulate or adhere to the side walls. Steps (C) and (D) were performed in the same manner as in Example 11 to obtain a product yield of 93%. The epoxy equivalent of this product is 146, and the turbidity of kaolin melted at 14 ° C is 1 or less. The epoxy equivalent after heating at 150 ° C for 24 hours in a sealed container is 148. The calculation found that the epoxy equivalent change caused by heating was 1.4%. Step (E) was performed in the same manner as in Example 11 and the product yield was 75%. Example 1 3 The scale of Example 6 was increased by 100 times. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) The reactor used is made of stainless steel, with an internal volume of 200, and it has two 60 cm long and 4 cm wide 4mm thick bezel. The agitator used includes a rotating shaft and two flat blades fixed on the shaft. The two-plane blades are symmetrically arranged in the plane of the rotation axis. Two-thirds of the blades are formed by a grid and two-thirds of the blades are formed by a paddle. The width of the stirrer is 0. 5 3 times the internal diameter of the reactor. When the agitator is submerged in the liquid of the reactor and rotates, the lower part of the paddle forces the liquid at the bottom of the reactor to flow to the lower half of the side wall and forms a layered circulating flow, rising along the side wall of the reactor to the liquid surface In the standard of liquid paper, the Chinese National Standard (CNS) A4 specification (210X297 mm) is applied. -47-487697 Printed by A7, B7 of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (45) Vortex down and cut the grid of the rotary stirrer into segments. Therefore, when the agitator is continuously rotated, the liquid remains uniform under agitation. The agitation causes the liquid to generate a circulating flow, rises along the bottom of the reactor inner wall to the surface of the slurry, and turns from an ascending flow to a swirl at the surface Downflow and cut the vortex into fragments. Step (A) proceeds smoothly in the same manner as in Example 6. In step (B), the reaction mixture is kept homogeneous by stirring, unlike Example 11, which does not cause precipitation of sodium chloride to accumulate or adhere to the side walls. Step (C) was performed in the same manner as in Example 6. Step (D) was performed in the same manner as in Example 6 to obtain a product with a yield of 90%. The epoxy equivalent of this product is 102, and the turbidity of kaolin melted at 14 ° C is 1 or below. The epoxy equivalent after heating at 150 ° C for 24 hours in a sealed container is 103. . The calculation found that the epoxy equivalent caused by heating was changed to Γ%. Step (E) was carried out in the same manner as in Example 6 and the product yield was 82%. The epoxy equivalent of this product is 99, and the epoxy equivalent is the same even if it is heated at 150 ° C for 24 hours in a sealed container. Example 1 4 Step (A): A 20 liter glass reaction flask equipped with a paddle stirrer was charged with 300 g of water, 55 g of tetramethylammonium chloride, 13 · 88 g (150 mo) epichlorohydrin, and 1.29 g ( 10 m 0j?) Cyanuric acid to form a reaction mixture. The reaction mixture in the flask was then heated with stirring to raise its temperature. When the temperature of the reaction mixture reaches 8 9 ° C, the paper size of the reaction mixture is in accordance with Chinese National Standard (CNS) A4 (2! 〇χ297 mm) (Please read the precautions on the back before filling in this page) 487697 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Invention Description (46) Boiling under atmospheric pressure. Heating was continued for 5 hours' to evaporate with the condenser cooling, and the liquefied epichlorohydrin was continuously returned to the flask, and the liquefied water was discharged from the flask. When the temperature of the reaction mixture reached 120 ° C, the heating was stopped, and the reaction mixture was cooled at 45 ° C to obtain a reaction product. No unreacted cyanuric acid was detected in this product. Step (B): Then, 2 · 56 kg (in terms of NaOH as 3 · 2moj?) Of 50wt% sodium hydroxide was added dropwise to the entire reaction mixture maintained at 50 ° C in a flask, which was at 10 Starting at 0 imn H g under reduced pressure, a reaction mixture was formed, while water and epichlorohydrin were evaporated from the reaction mixture with vigorous stirring. Gradually increase the vacuum while cooling with a condenser, and continuously return all liquefied epichlorohydrin to the flask, and drain the liquefied water out of the flask. When the degree of vacuum reaches 60 legs of Hg, the solution is added dropwise at the end to prepare a solution containing precipitated sodium chloride. This dropwise addition takes 6 hours. After refluxing for another 5 minutes, the vacuum in the reactor was released and stirring was stopped. According to the liquid chromatography analysis, the obtained slurry contained a compound having 2-carboxyl-3-chloropropyl group at a content of 1 wt% or less. Steps (A) and (B) were repeated 4 times, and the whole slurry was used as step (C). Step (C): The above slurry is gently stirred with 245 distilled water and 80 g of sodium toluenesulfonate in a container, so that the sodium chloride precipitated in the slurry is dissolved in the added water, the liquid is left in the container, and then The entire organic layer was recovered to obtain a transparent liquid product. A cleaning device is installed to clean the liquid product with droplets. The paper size of this cleaning device is applicable to the Chinese National Standard (CNS) A4 specification (21GX297 mm)-installed-(Please read the precautions on the back before filling out this page) Order-49-487697 Employees' Cooperatives, Central Standards Bureau, Ministry of Economic Affairs Printed A7 * ___________B7 _ V. Description of the invention (47) Including glass main cylinder with 30 legs high and 50 diameter inner diameter, cylinder storage connected to the upper end of the main cylinder, and the other with the lower end of the main cylinder A connected cylindrical reservoir covers a cover of the upper reservoir and a rotating shaft extending through the center of the cover to the lower end of the main cylinder. The inner diameter of the upper reservoir is almost the same as that of the main cylinder, with a height of 160 legs and a discharge hole above. A liquid supply pipe extending to the lower end of the upper reservoir is installed through the cap. The inner diameter of the lower reservoir is almost the same, with a depth of 160 legs and a drainage hole at the bottom. In the middle of the lower reservoir, there is a liquid supply pipe extending through the side wall to near the lower end of the rotating shaft. Around the rotating shaft, from the lower end of the shaft to the upper end of the main cylinder, six discs with a large number of holes are mounted at a fixed pitch. On the inner wall of the main cylinder, a 15-band wide ring baffle is inserted between each disc. Each disc has a diameter of 40 legs and a hoop is mounted below the circumference of each disc. Each disc opens a plurality of holes with a diameter of 2 nun, and passes through the holes from the upper surface to the lower surface. When the rotary shaft is driven by a drive system connected to its top end, it rotates alternately. The liquid product was introduced into the cleaning device until the upper reservoir was half full, and the rotary shaft was rotated at a speed of 110 revolutions per minute. An aqueous solution containing 0.333% by weight of sodium toluenesulfonate and 3wt% of sodium dihydrogenphosphate was supplied at a feed rate of 0.078 liters / minute. The aqueous solution that had been in contact with the liquid product began to be discharged through the discharge hole of the upper reservoir After the liquid product is discharged from the bottom of the lower reservoir, the unrefined liquid product is supplied through a liquid supply pipe above the cleaning device at a rate of 0.51 / min. After the liquid product started to be discharged, it was immediately returned to the storage tank for the liquid product because it was unprepared. It was observed that the supplied aqueous solution was dispersed in the epichlorohydrin layer, forming droplets having a volume of about 0.3 to 7 legs. The size of the refined paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before filling this page) and fill in the items. Packing. -50-487697 A7 * __B7 V. Description of the invention (48) After the liquid starts to be discharged, collect 20 j? The discharged liquid is a refined liquid. Next, the purified liquid was washed with a sodium toluenesulfonate aqueous solution of 0. 0 3 wt.%. The refined liquid and the aqueous solution were respectively supplied at a feed rate of 0.45 5 / min and 0. 19 P / min, and the rotating shaft was rotated at a speed of 110 revolutions / min to obtain a second transparent liquid. The epichlorohydrin layer obtained in the second washing was collected as a refined liquid refined in step (C). The refined liquid contained 83% twt of epichlorohydrin. Step (D): Introduce 2 $ part of the refined liquid collected in step (C) into a 10 P rotary evaporator. Evaporation of epichlorohydrin begins at a temperature of 60 ° C under reduced pressure. When the vacuum gradually decreases to 2 legs H g and the temperature rises to 140 ° C, evaporation continues. The epoxy equivalent of the product obtained by cooling the liquid was 10 2 0. Example 15 The steps (A) to (C) of Example 6 were performed on a scale of 10 times, and printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. (Please read the precautions on the back before filling this page) Step (D): Process the refined liquid collected in step (C) in a flask evaporator to obtain a concentrated solution with an epichlorohydrin concentration of 70 wt%. Epichlorohydrin was removed from the purified liquid by a membrane evaporator to obtain a product of triglycidyl isocyanurate with a reduced epichlorohydrin concentration. The evaporator used includes a cylinder with a diameter of 3,15 mm and a height of 7,35, which is covered by a cap having a liquid inlet and a vapor outlet and a liquid outlet at the bottom. The cylinder is surrounded by a sleeve to circulate the heat medium, and the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -51-487697 A7 — B7 V. Description of the invention (49) The cylinder passes the steam outlet Connected with a vacuum pump with a condenser. In the cylinder, there is a rotating shaft agitated through the cover, a disk having a diameter of 275 above the shaft, and an applicator under the disk, the applicator extending through the shaft. It is supported by the rod end bracket. The applicator is installed so that it is pressed against the inner wall of the cylinder by centrifugal force, and slides along the inner wall of the cylinder when the rotary shaft rotates. The shape of the applicator is a rectangular parallel tube of 60 legs, and a flat surface with a vertical width of 20 legs faces the cylinder. From the top to the bottom of the flat surface, a plurality of grooves are cut at a distance of 12 legs, which are staggered with the surface at an angle of 45 ° with respect to the vertical. The groove is 8 legs deep and 12 mm wide. The heated steam was introduced into the evaporator sleeve, the rotating shaft was rotated at a speed of 200 r pm, and the vacuum was operated to maintain a reduced pressure of 10 mm H g. The liquid product concentrate with an epichlorohydrin concentration of 7 Ow t% was sent to the evaporator at a rate of 22.4 kg / h with a film thickness of 230 // m and an average residence time of 15 seconds. The bottom outlet collection temperature was 1 2 3 ° C, the epoxy equivalent was 103 and the product contained 2 500 ppm epichlorohydrin. The prepared product is a transparent liquid and contains no insoluble matter. Printed again by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Steamed Economy (please read the precautions on the back before filling this page). The sender processes the prepared liquid product to produce a product with a lower concentration of chlorohydrin. 2 In the batch, the heat medium was introduced into the sleeve, the rotary shaft was rotated at 200 r pm, and the vacuum pump was operated to maintain a decompression of 0 · 2 nun H g. The liquid of the above epichlorohydrin concentration of 2 50 0 p pm was supplied at a rate of 14 · Okg / h, the film thickness was 17 0 / zm, the average residence time was 18 seconds, and the recovery temperature from the outlet at the bottom of the evaporator was 1 5 5 ° C, epoxy equivalent is the standard of this paper. Chinese National Standard (CNS) A4 specification (210X297 mm) -52-487697 A7 B7 V. Description of invention (50) 1 0 3 and 5 4 P pm table Product of chlorohydrin. The recovered product is a transparent liquid, which contains no insoluble matter. Based on the raw material isocyanuric acid, the yield of triglycidyl isocyanurate was 90%. Step (E): 100 g of the epichlorohydrin concentration of 5 4 P pm obtained in step (D) is gradually added to the methanol in a 400 g beaker under stirring to form a product solution in methanol. The solution was heated to the reflux temperature of methanol and then cooled to 5 ° C within 12 hours. White crystals precipitated in the solution. The white crystal was separated by filtration, and then dried to obtain 8 2 g of a final product having an epoxy equivalent of 9 9. Example 16 A slurry containing precipitated sodium chloride was prepared in the same manner as in steps (A) and (B) of Example 13. The entire slurry was then treated at an increasing rate in the same manner as in step 14 (C) of Example 14. The precipitated sodium chloride was removed from the slurry by dissolution to obtain a liquid product. The liquid product was first washed with a sodium toluenesulfonate and an aqueous sodium hydrogen phosphate solution using a cleaning device, and then the liquid product was washed with an aqueous sodium toluenesulfonate solution to obtain a refined liquid. . The purified liquid was concentrated by a flask evaporator to obtain a concentrated liquid 'epichlorohydrin was removed using a membrane evaporator in the same manner as in step 5 of Example 1 to obtain 27 · 0 kg of epoxy equivalent 101 and epichlorohydrin concentration 8 The product of 0 p pm. Example 1 7

Steps (A) and (B) •• Steps (A) and (B of this example & Zhang scales are applicable to Zhongguanjia Standard (CNS) A4 specification (2lGx297)) in Example 1 (Please read the precautions on the back before (Fill in:: write this page) Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs-53-487697 A7 * _B7 V. Description of Invention (51)) The same procedure was used to prepare a precipitated sodium chloride slurry. Step (C): For the first time, the slurry was washed with distilled water in the same manner as in Example 1 without using a refining agent. The second washing was performed in the same manner as in Example 1, but 2 g of sodium cinnamate was used instead of 2 g of sodium tosylate. The final washing was performed in the same manner as in Example 1, but a purified liquid was prepared using an aqueous solution of 0.1 g of sodium cinnamate in 800 g of distilled water. Step (D): The entire final epichlorohydrin layer obtained in step (C) was treated in the same manner as in step (D) of Example 1, so 257 g of the product was recovered from the evaporator. Ionic chloride was not measured in this product. The epoxy equivalent of this product was the same as that obtained in Example 1. The turbidity of the kaolin melted at 140 ° C was the same. It was heated at 150 ° C in a sealed container. 2 The epoxy equivalent was the same after 4 hours. Example 18 Steps (A) and (B): A precipitated sodium chloride-containing slurry was prepared in the same manner as in steps (A) and (B) of Example 1. Printed by the Consumer Cooperative of the Central Bureau of Accreditation of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Step (C): For the first time, wash the slurry with distilled water in the same manner as in Example 1, without using the refined preparation. The second washing was performed in the same manner as in Example 1, but 2 g of a sodium sulfonate formaldehyde condensate known as a water-soluble water reducing agent was used instead of 2 g of sodium toluenesulfonate. The final cleaning was performed in the same manner as in Example 1, but using 0.1 g of sodium formaldehyde sulfonate formaldehyde condensate in 800 g of distilled water. The paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm). ) -54-487697 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (52) A refined liquid was prepared from the solution. Step (D): The entire final epichlorohydrin layer obtained in step (c) was treated in the same manner as in step (D) of Example 1, so 257 g of the product was recovered from the evaporator. Ion chloride was not measured in this product. The epoxy equivalent of this product was the same as that obtained in Example 1. The turbidity of kaolin melted at 140 ° C was the same. It was heated at 150 ° C in a sealed container. 2 The epoxy equivalent was the same after 4 hours. Example 19 Steps (A) and (B): A precipitated sodium chloride-containing slurry was prepared in the same manner as in steps (A) and (B) of Example 1. Step (C): For the first time in the same manner as in Example 1, but using 0.1 g of disodium phthalate instead of 2 g of sodium tosylate. The second washing was carried out in the same manner as in Example 1, except that 0.5 g of disodium phthalate was used instead of 2 g of sodium tosylate. The final washing was performed in the same manner as in Example 1, but a purified liquid was prepared using an aqueous solution of 0.1 g of disodium phthalate in 800 g of distilled water. Step (D): The entire final epichlorohydrin layer obtained in step (C) was treated in the same manner as in step (D) of Example 1, so 257 g of the product was recovered from the evaporator. Ionic chloride was not measured in this product. The epoxy equivalent of this product was the same as that obtained in Example 1. The turbidity of the kaolin melted at 140 ° C was the same. It was heated at 150 ° C in a sealed container. 2 The epoxy equivalent was the same after 4 hours. This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm)-installed-(Please read the precautions on the back before filling this page)

1T-55-487697 A7 B7 V. Description of the invention (53) Example 20 (Please read the precautions on the back before filling this page) Steps (A) and (B): Step 1 (A) and Example 1 (B) A slurry containing precipitated sodium chloride was prepared in the same manner. Step (C): For the first time in the same manner as in Example 1, but replacing 2 g of sodium toluate with 0.2 g of disodium salicylate. The second washing was performed in the same manner as in Example 1 except that 2 g of sodium tosylate was replaced with 0.5 g of disodium salicylate. The final cleaning was performed in the same manner as in Example 1 to prepare a refined liquid. Step (D): The entire final epichlorohydrin layer prepared in step (C) was treated in the same manner as in Step (D) of Example 1, and thus self-evaporated. The device recovered 2 5 7 g of product. Ionic chloride was not measured in this product. The epoxy equivalent of this product was the same as that obtained in Example 1. The turbidity of the kaolin melted at 140 ° C was the same. It was heated at 150 ° C in a sealed container. 2 The epoxy equivalent was the same after 4 hours. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economics Example 2 1 Steps (A) and (B): A precipitated sodium chloride-containing slurry was prepared in the same manner as in steps (A) and (B) of Example 1. Step (C): For the first time, the slurry was washed with distilled water in the same manner as in Example 1 without using a refining agent. The second washing was performed in the same manner as in Example 1, but 2 g of sodium laurate was used instead of 2 g of sodium tosylate. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -56-487697 A7 B7 V. Description of the invention (54) The final cleaning is performed in the same way as in Example 1, but using 0.2 g of sodium lauryl sulfate in 800 g of an aqueous solution in distilled water was used to prepare a refined liquid. Step (D): The entire final epichlorohydrin layer obtained in step (c) was treated in the same manner as in step (D) of Example 1, so 257 g of the product was recovered from the evaporator. Ion chloride was not measured in this product. The epoxy equivalent of this product was the same as that obtained in Example 1. The turbidity of kaolin melted at 140 ° C was the same. It was heated at 150 ° C in a sealed container. 2 The epoxy equivalent was the same after 4 hours. Example 2 2 Example 1 1 was repeated, in which terephthalic acid was used as a raw material, and the reactor of steps (A) and (B) of Example 13, the cleaning device of Example r 4 step (C), and the example were used. The 15-step (D) film evaporator will be enlarged 10 times. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) Step (A) can be performed smoothly in the same way as in Example 11. Step (B) is performed. Unlike Example 11, sodium chloride accumulation does not occur or it adheres to the side wall, and the reaction mixture is maintained uniform as a whole. The final reaction mixture was recovered as a slurry. Step (C) is performed without using a refining agent. After adding 60 kg of distilled water ', the whole slurry was gently stirred in a container to dissolve the sodium chloride precipitated in the slurry into the added water and left for 12 hours. The whole organic layer was recovered to obtain a transparent liquid product. The first cleaning was performed in the same manner as in Example 14 and the liquid product was washed with distilled water. The liquid product and the cleaned distilled water were used to supply the Chinese standard (CNS) A4 specification (210X297 mm) to this scale.--57 -487697 A7 B7 V. Description of the invention (55) It should go to the cleaning device to obtain a transparent refined liquid. The recovered liquid was washed once with distilled water to obtain the refined liquid of step (C). Step (D) was performed in the same manner as in Example i5. The refined liquid was first processed in a flash still to obtain a concentrated solution having an epichlorohydrin concentration of 70 wt%, and the concentrated solution was supplied to an evaporator. The first treatment was performed under an average reduced pressure of 1 OirnnHg , The film thickness is 2 2 0 // m, the average residence time is 15 seconds, and the product with an epichlorohydrin content of 2 600 ppm and 12 0 ° C is obtained from the outlet at the bottom of the evaporator. The decompression is 0 · 2ramHg, the film thickness is 180 // m, the average residence time is 18 seconds, and 2 5 · 8kg epichlorohydrin content is 60 p ppm and 1 5 5 ° from the outlet at the bottom of the evaporator. The product of C. The resulting product has an epoxy equivalent of 1 4 6 and is a transparent liquid containing no insoluble matter. Example 2 3 The steps (A) and (B) were performed using the reactor used in Example 13 and the step (D) was performed using the film evaporator used in Example 15. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Step (A): Mix 1000g of water, 250g of sodium bromide as a catalyst, 92 · 5kg of epichlorohydrin and · 3 kg of terephthalic acid to form a reaction mixture. The reaction mixture was heated to 120 ° C over 12 hours, and the liquefied epichlorohydrin was returned to the reactor under reflux and the liquefied water was discharged from the reactor. The reaction mixture began to boil at 90 ° C under atmospheric pressure. When the temperature of the reaction mixture reached 120 ° C, the heating was stopped and then cooled to 45 ° C to prepare a reaction product. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ~---58-487697 A7 · _____B7 V. Description of the invention (56) Step (B): In maintaining the overall reaction product at 45 ° C, In a stirring state, 8.8 kg of a 50 wt% sodium chloride aqueous solution was added dropwise over 6 hours, and water and epichlorohydrin were evaporated from the formed reaction mixture, the epichlorohydrin was refluxed, and water was discharged from the reactor. The addition was started by reducing the pressure to 100 Hg and gradually increasing the degree of vacuum. During the addition, due to the precipitation of sodium chloride, the reaction mixture became cloudy with stirring, but the whole was kept uniform. This resulted in a final slurry without precipitated sodium chloride accumulating or sticking to the side walls of the reactor. Step (C): After adding 3 kg of distilled water, gently stir the whole slurry in a container and leave it for 12 hours. The recovered organic layer was in the form of a transparent liquid, which contained no precipitated sodium chloride. Then, 3 kg of a 5 wt% sodium dihydrogen phosphate aqueous solution was added to the overall transparent liquid, and the resulting mixture was stirred and left for 6 hours. The organic layer was recovered as a refined transparent liquid. 3 kg of distilled water was again added to the overall transparent liquid, and the mixture was stirred and allowed to stand for 6 hours. The organic layer was recovered as a purified transparent liquid. It is generally believed that a transparent organic layer can be obtained by performing the above-mentioned cleaning effect using water without using a refined preparation, which is attributed to the catalyst used in step (A). Step (D) was performed in the same manner as in Example 15. The refined liquid was first processed in a flash still to obtain a concentrated solution having an epichlorohydrin concentration of 70 wt%, and the concentrated solution was supplied to an evaporator. The first treatment was performed at an average reduced pressure of 10 ram Hg Below, the film thickness is 2 2 5 // m, the average retention time is 16 seconds, and the product with an epichlorohydrin content of 2 4 0 0 p pm and 1 2 0 ° C is obtained from the outlet at the bottom of the evaporator. The average decompression of the secondary treatment is 0 · 2ramHg, the film thickness is 175 // m, and the average retention time is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm).

(Please read the notes on the back before filling in I: Write this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -59-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 487697 A7 B7 V. Description of the Invention For 20 seconds, 11.4 kg of epichlorohydrin with a content of 50 p pm and a temperature of 15 5 ° C was prepared from the outlet at the bottom of the evaporator. The obtained product has an epoxy equivalent of 153, which is a transparent liquid containing no insoluble matter. Example 2 4 Step (A): A reactor equipped with a stirrer as used in Example 13 was arranged. The reactor was charged with 3 kg of water, 550 g of tetramethylammonium chloride, 1 38 · 8 kg of epichlorohydrin, and 1 2 · 9 kg of cyanuric acid, and stirred to form a reaction mixture. The reaction mixture in the flask was then heated with stirring to raise its temperature. When the temperature of the reaction mixture reached 89 ° C, the reaction mixture began to boil at atmospheric pressure. The heating was continued for 5 hours, and the evaporation generated by the condenser was cooled, and the liquefied epichlorohydrin was continuously returned to the flask, and the liquefied water was discharged from the flask. When the temperature of the reaction mixture reached 120 ° C, the heating was stopped, and the reaction mixture was cooled at 45 ° C to obtain a reaction product. Analysis by liquid chromatography confirmed that the reaction product did not contain unreacted cyanuric acid because of the raw material phthalic acid. Step (B): Then, 25.6 kg of 50 wt% sodium hydroxide was added dropwise to the entire reaction mixture maintained at 50 ° C in the flask, which started under reduced pressure of 100 legs H g to form A reaction mixture from which water and epichlorohydrin are evaporated. Gradually increase the degree of vacuum while cooling it with a condenser, and continuously return all liquefied epichlorohydrin to the reactor, and discharge the liquefied water out of the reactor. When the vacuum reaches 6 OnmiHg, the paper size is applicable to the Chinese National Standard (CNS) 8-4 specifications (210 X 297 mm) --- τ --- clothing ------ 1T ------ (please first Read the notes on the back and fill in this page again)-60-487697 A7 B7 5. When the invention description (58) 'End drop-adding effect, a solution containing precipitated sodium chloride is prepared. The dropwise addition took 6 hours. During the addition, the reaction mixture became cloudy with stirring due to the precipitation of sodium chloride, but the whole was kept uniform. This reflux was maintained for another 5 minutes, then the vacuum in the reactor was released and stirring was stopped. According to liquid chromatography analysis, the prepared slurry contained less than 1 wt% of a compound having 2-carboxyl-3-chloropropyl. Step (C): The whole slurry obtained in the cleaning step (B) is washed 3 times. It was first stirred with 90 kg of water and then left for 24 hours. Next, it was stirred with 15 kg of 5 w t% sodium dihydrogen phosphate, and then left for 24 hours. Finally, stir with 90 kg of water and leave it for 24 hours. The final epichlorohydrin layer was recovered as a refined liquid. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Step (D): Import the entire epichlorohydrin layer prepared in step (C) into the rotary evaporator one by one Epichlorohydrin was removed by heating under reduced pressure. Before the evaporation stopped, the legs were heated at 140 ° C for 1 hour under a reduced pressure of 2 Hg. Cooling to room temperature and recovering the contents of the evaporator yielded 26.7 kg of product. Calculating the amount of the product based on the cyanuric acid used as the raw material in step (A), it was found to be equivalent to 90% yield. This product has an epoxy equivalent of 104 and melts at 140 ° C to form a transparent liquid. Step (E): Melt the product obtained in step (D). Under stirring in the flask, 100 g of the melt is gradually added to 400 g of methanol to form a solution of the product in methanol. The solution was heated to the reflux temperature of methanol and then cooled to 5 ° C within 12 hours. White crystals precipitated in the solution. This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) -61-487697 A7 _ ___ B7 V. Description of the invention (59) White crystals are separated by furnace action, and then dried to obtain 8 2 g final product . The epoxy equivalent of the final product was 100. Comparative Example 3 Steps (a) and (B) were performed in the same manner as in Example 24, but the reactor had a paddle. In step (B), the precipitated sodium chloride adheres to the side wall of the reactor 'so that the reaction mixture cannot be maintained homogeneous. Steps (C) and (D) were performed in the same manner as in Example 24, and 25.2 kg of product was recovered from the evaporator. The epoxy equivalent of the product was 109. The product was treated in the same manner as in step (E) of Example 24 to obtain 80 g of white crystals, which was a dry final product. The epoxy equivalent of the final product was 101. Example 2 5 Step (A): A 20 glass reaction flask equipped with a paddle stirrer was charged with 300 g of water and 55 g of tetramethylammonium chloride, printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read first Note on the back page, please fill in this page again) 13 · 88kg of epichlorohydrin and 1.29g of cyanuric acid to form a reaction mixture. The reaction mixture in the flask was then heated with stirring to raise its temperature. When the temperature of the reaction mixture reached 89 ° C, the reaction mixture began to boil at atmospheric pressure. The heating was continued for 5 hours, and the evaporation produced by the condenser cooling was continuously returned to the flask, and the liquefied water was discharged from the flask. When the temperature of the reaction mixture reaches 120 ° C, stop heating and cool the reaction mixture at 45 ° C to produce a reaction product. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). -62-487697 A7, ____B7_ 5. Description of the invention (60). No unreacted cyanuric acid was detected in this product. Step (B): Then, 2.56 kg of 50 wt% sodium hydroxide was added dropwise to the entire reaction product maintained at 50 ° C, which started under reduced pressure of 100 leg Hg to form a The reaction mixture was simultaneously evaporated with water and epichlorohydrin from the reaction mixture. Gradually increase the vacuum while cooling it with a condenser, return all liquefied epichlorohydrin to the flask continuously, and drain the liquefied water out of the flask. When the degree of vacuum reaches 60 nun H g, the dropwise addition is ended to prepare a solution containing precipitated sodium chloride. The dropwise addition took 6 hours. Reflux for another 5 minutes, release the vacuum in the reactor, and stop stirring. According to liquid chromatography analysis, the prepared slurry contained less than 1 wt% of a compound having a 2-carboxyl-3-chloropropyl group. Steps (A) and (B) were repeated 4 times, and the entire slurry was used in step (C). Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Step (C): Stir the liquid product and 24 5 distilled water in a container to make the sodium chloride precipitated in the liquid product It was dissolved in added water, and the liquid in the container was set aside, and then the entire liquid product layer was recovered to obtain a partially refined liquid product. The cleaning apparatus used in Example 14 was arranged to further refine the liquid product. The part of the refined liquid product was introduced into the cleaning device until the upper reservoir was half full, and the rotary shaft was rotated at a speed of 110 revolutions per minute. An aqueous solution containing 3% by weight of sodium dihydrogen phosphate is supplied at a feed rate of 0 · 07 8 1 / min. The aqueous solution that has been in contact with the liquid product begins to apply the Chinese National Standard (CNS) A4 specification (210X297 mm) through this paper standard. -63-487697 A7-___B7 V. Description of the invention (61) After the discharge hole of the upper reservoir is discharged, the liquid product is discharged from the bottom of the lower reservoir, and is supplied through the liquid supply pipe above the cleaning device at a rate of 0.5 · 1 1 Unrefined liquid product. After the liquid product started to be discharged, it was immediately returned to a storage tank for partially purified liquid product because it was not refined. It was observed that the supplied aqueous solution was dispersed in the epichlorohydrin layer, forming droplets having a volume of about 0.3 to 7 mm. After the refined transparent liquid starts to be discharged, the discharged liquid is collected as a refined liquid. Next, the purified liquid was washed with distilled water. The refined liquid and the aqueous solution were supplied at a feed rate of 0.455 / min and 0.19 L / min, respectively, and the rotating shaft was rotated at a speed of 1 10 revolutions / min to obtain a second transparent liquid. The epichlorohydrin layer obtained in the second washing was collected as a refined liquid refined in step (C). The yield of the triglycidyl isocyanurate was 90%. Step (D): The purified liquid collected in 2 and part of Step (C) was introduced into a 10 j? Rotary evaporator. Evaporation of epichlorohydrin 'starts at 60 ° C under reduced pressure. When the degree of vacuum gradually decreases to 4 ° Hg and the temperature rises to 150 ° C, evaporation continues. This liquid contained 5,000 p pm epichlorohydrin 'epoxy equivalent of 104. The product was transparent when melted at 140 ° C. Example 2 6 A liquid product containing precipitated sodium chloride was prepared in the same manner as in step 2 (5) of Example 2 except that 55 g of ethyltriphenylphosphonium bromide was used instead of 55 g of tetramethylammonium chloride. . Repeat steps (a) and (b) 4 times. This paper size applies the Chinese National Standard (CNS) M specification (21〇 × 297 mm) — -64 — (Please read the notes on the back before filling in .: Write this page} Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 487697 A7 B7 V. Description of the invention (62), all the paddle fluid produced is used in step (C). Step (c) is performed in the same manner as in Example 25. First produced The partially refined liquid product was then highly refined using the same cleaning device of Example 14. In the first cleaning in the cleaning device, the rotary shaft was continuously rotated at a speed of 90 rpm. At 0 · 0525 The feed rate per minute supplies an aqueous solution containing 3 wt% of sodium dihydrogen phosphate through the liquid supply line of the lower reservoir. After the aqueous solution that has been in contact with the liquid product begins to be discharged through the discharge hole of the upper reservoir, the liquid product comes from below The bottom of the reservoir is discharged, and the partially refined liquid product is supplied through the liquid supply pipe above the cleaning device at a rate of 0.345 / min. After the liquid product starts to be discharged, it is immediately returned to the liquid product for use. Storage tank. It was observed that the supplied aqueous solution was dispersed in the epichlorohydrin layer, forming droplets with a volume of about 0.3 to 7 legs. After the highly refined transparent liquid began to be discharged, the entire discharged liquid was collected, which was a highly refined liquid. Printed by the Ministry of Standards and Staff ’s Consumer Cooperatives (please read the precautions on the back before filling out this page) Secondly, wash the highly refined liquid with distilled water. The refined liquid and aqueous solution are respectively 0 · 305 / min and 0 · 13W / min The feed rate is supplied, and the rotating shaft is rotated at a speed of 90 revolutions per minute to obtain a second transparent liquid. The epichlorohydrin layer obtained in the second cleaning is collected for refining after step (C) Liquid. Step (D): Evaporating epichlorohydrin 'from the liquid collected in step (c) in the same manner as in Example 25 to prepare a liquid product at a reduced pressure of 4 nun H g 1 5 Ot. This liquid contains 4 6 0 ppm Table Chlorohydrin, and the epoxy equivalent is 105. The product is transparent when melted at 140 ° C. ^ The paper size applies the Chinese National Standard (CNS) A4 specification (210X297), ^-~ -65-487697 Central Ministry of Economic Affairs Standard Bureau staff consumption Printed by the cooperative A7 B7 V. Description of the invention (63) Example 2 7 Step (A): 300 g of water and 55 g of tetramethylammonium are placed in a 20 $ glass reaction flask equipped with a stirrer with paddles and baffles Chlorine, 13.88 kg of epichlorohydrin and 1.29 kg of chlorouric acid form a reaction mixture. The reaction mixture in the flask is then heated with stirring to raise its temperature. When the temperature of the reaction mixture reaches 8 9 ° C, the The reaction mixture began to boil under atmospheric pressure. The heating effect continued for 5 hours, and the evaporation generated by the condenser cooling was continuously returned to the flask, and the liquefied water was discharged from the flask. When the temperature of the reaction mixture reached 120 ° C, the heating was stopped, and the reaction mixture was cooled at 45 ° C to obtain a reaction product. No unreacted osmic acid was detected in this product. Step (B) •• Then, 2.56 kg of 50 wt% sodium hydroxide was added dropwise to the entire reaction mixture maintained at 50 ° C in the flask, which was started under reduced pressure of 10 OramHg to form A reaction mixture from which water and epichlorohydrin are evaporated. Gradually increase the degree of vacuum while cooling it with a condenser, and continuously return all liquefied epichlorohydrin to the reactor, and discharge the liquefied water out of the reactor. When the degree of vacuum reaches 600 mbar Hg, the dropwise addition is ended to prepare a solution containing precipitated sodium chloride. The dropwise addition took 6 hours. During the addition period ', the reaction mixture became cloudy with stirring due to the precipitation of sodium chloride, but the whole was kept uniform. This reflux was maintained for another 5 minutes, then the vacuum 'in the reactor was released and stirring was stopped. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -66 A ---- ^ 1-J--J--ϋ-(Please read the precautions on the back before filling this page) Order 487697 A7 B7 V. Description of the invention (64) According to liquid chromatography analysis, the prepared slurry contains less than 1 W t% of compounds having 2-carboxy-3-chloropropyl groups. (Please read the precautions on the back before filling this page) Step (C): Wash the whole slurry 3 times in the cleaning step (B). Stir with 6 kg of distilled water first, then leave for 24 hours. Next, it was stirred with 6 kg of 5 w t% sodium dihydrogen phosphate, and then left for 24 hours. Finally, it was stirred with 8 kg of distilled water and allowed to stand for 24 hours. The final epichlorohydrin layer 'was recovered as a refined liquid product. Step (D): The liquid product obtained in step (C) is processed in a flash still to obtain a concentrated solution having an epichlorohydrin concentration of 50 wt%. Epichlorohydrin was evaporated from the concentrated liquid film using the evaporator used in Example 15 to obtain an isocyanuric acid triglycidyl ester product having a reduced epichlorohydrin concentration. Based on the raw material isocyanuric acid, the yield of the triglycidyl isocyanate was 90%. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Introduce the heated steam into the evaporator sleeve, rotate the rotary shaft at 200 r pm, and start the vacuum extractor. A concentrated liquid product with a concentration of 50% of chlorohydrin produced in the flash evaporator was supplied to the evaporator. The evaporator is operated at the feed rates and vacuum levels shown in Table 1. The average film thickness (V) retention time is shown in the table. The products (Pi) and (P2) are recovered from the outlet at the bottom of the evaporator. For the bottom outlet temperature of the evaporator, the epoxy equivalent and epichlorohydrin concentration (E CHp pm) are shown in the table. The recovered products are transparent liquids without insoluble matter. Then, the liquid product (Pi) was recovered in an evaporator to obtain a product (Qi) having a lower epichlorohydrin concentration. This time, the liquid was supplied at a feed rate of 14.0 kg / hr, and the rotary shaft was rotated at a speed of 200 rpm. Operate the evaporator with the vacuum degree shown in Table 1. The film thickness (V) of this paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm). 67-487697 A7 __ B7 V. Description of the invention (65) The average retention time is shown in the table. The product (Q 1) is recovered from the bottom outlet of the evaporator, which has the temperature at the bottom outlet of the evaporator. The recovered product is a transparent liquid containing no insoluble matter. : Pack II (Please read the precautions on the back before filling this page)

1T it Printed by the Consumer Cooperatives of the Central Standard Bureau of the Ministry of Economy

Centimeter 7 487697 A7 B7 V. Description of the invention (66) Table 1 Evaporation conditions and product properties printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs P 1 P 2 Q 1 Supply of liquid concentrate concentrate P 1 Feed rate (kg / hr ) 21.7 7,3 14.0 Vacuum (nun H g) 10 10 0.2 Film thickness (//) 450 150 170 Retention time (seconds) 15. 15 18 Product temperature at outlet (° C) 120 137 150 Product epoxy equivalent 103 103 103 E CH concentration of the product (p pm) 3 8 0 0 2 0 0 0 80 (Please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) ) -69-487697 A7 B7 V. Description of the invention (67) Step (E) • • Melt in a flask and stir 100g of the product obtained in step (D) (Qd melt is gradually added to 400 g of methanol, A solution of the product in methanol was formed. The solution was heated to the reflux temperature of methanol and then cooled to 5 ° C within 12 hours. White crystals precipitated in the solution. The white crystals were separated by filtration and then dried to obtain 8 2 g The final product (Zι) has an epoxy equivalent of 99. Example 4 A refined liquid product was prepared in the same manner as steps (A) to (C) in Example 27, and then processed in a flash evaporator to obtain a concentrated solution having an epichlorohydrin concentration of 50 wt%. Central Standard of the Ministry of Economy Printed by the Bureau ’s Consumer Cooperatives (please read the precautions on the back before filling out this page) Secondly, import 5kg of concentrated liquid into a 10 $ rotary evaporator 'reducing the pressure with 1 0 0 leg Hg at 60 ° C to remove the table Chlorohydrin. When removing epichlorohydrin, gradually increase the vacuum and increase the temperature. After 4 hours of evaporation, the temperature of the liquid in the evaporator reaches 150 ° C under reduced pressure. The formed liquid contains 5 OOppm epichlorohydrin. And the epoxy equivalent is 104 ° at a lower pressure of 2 legs Hg at 160 ° C and then epichlorohydrin is evaporated for 4 hours. The liquid formed contains 2000 p pm epichlorohydrin, and the epoxy equivalent increases to 10 7 ° Example 2 8 Example 2 was repeated using a reactor with a volume of 5m3, and Example 2 4 'was expanded by a factor of 25. Step (A) can be performed smoothly in the same manner as in Example 24. Steps This paper size applies Chinese national standards ( CNS) A4 specification (210X297 mm) -70-487697 A7 B7 Description (68) (B) in Comparative Example 3 with a different, and the reaction mixture was maintained uniform without adhesion of precipitated sodium chloride in the case of the reactor wall. Steps (C) and (D) were performed in the same manner as in Example 24 to obtain a product yield of 90%. The epoxy equivalent of this product was 104. Step (E) was performed in the same manner as in Example 24, and the yield was 82%. The epoxy equivalent of the product was 100. Example 2 9 A slurry containing precipitated sodium chloride was prepared in the same manner as in step (A) and (B) of Example 1 3. The whole slurry was gently stirred with 90 kg of water to dissolve the precipitated sodium chloride in the slurry into the added water, and the liquid in the container was kept. All the organic layers were recovered to obtain a transparent liquid. Then, the liquid was purified by using the cleaning device used in Step 14 (C) of Example 14. The liquid was firstly treated with an aqueous solution containing 3 wt% sodium dihydrogen phosphate and no toluenesulfonic acid, and then treated with distilled water to obtain a purified liquid. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Use the same method as described in step 15 of Example 15 at a higher rate to process the refined liquid in a flash evaporator. The film evaporator was used to remove epichlorohydrin to obtain a product with an epoxy equivalent of 104 and an epichlorohydrin concentration of 60 PP m. The product was transparent at 140 ° C. According to the present invention, a 2,3-epoxypropyl derivative or a 2-methyl-2,3-epoxypropyl derivative having 2 to 4 carboxyl compounds or 1 to 3 amido compounds can be prepared. As a purified product. The paper size of this product applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) -71-487697 A7 B7 V. Description of the invention (69) The product has a high oxygen oxide content and is quite transparent when melted Moreover, when the epoxy equivalent is not changed when heated at 150 ° C for 24 hours, its thermal stability is high. A product having such high purity and high thermal stability is suitable for a transparent sealant for a semiconductor device such as a light emitting device, a light intercepting device, or a photoelectric conversion device. According to the method of the present invention, the above-mentioned purified product can be produced with high production efficiency, such as high yield, high recovery rate of epihalohydrin or 2-methyl epihalohydrin in a short time, and the waste water produced in this method contains a small amount of epihalohydrin. Or 2-methyl epihalohydrin and epoxy compounds are easy to handle. (Please read the notes on the back before filling out this page) I # • Fill in the items. Pack-

, 1T

• Printed by the IAW Ministry of Economic Affairs Central Standards Bureau's Consumer Cooperative Cooperative This paper size applies to China National Standard (CNS) Α4 specification (210 × 297 mm) -72-

Claims (1)

487697 / f ν 'A8 B8 C8 D8 Attachment to the scope of patent application: No. 86109732 Patent Application Chinese Patent Application Amendment (please read the precautions on the back before filling out this page) Amended in December 1990 1 · There are 2 to 4 molecules in a production system Method for carboxyl or 2,3-epoxypropyl derivatives or 2-methyl-2,3-epoxypropyl derivatives of 1 to 3 amido compounds All hydrogen atoms are replaced by 2,3-glycidyl or 2-methyl-2,3-glycidyl, which is a purified product whose epoxy equivalent is 1 · 0 of the theoretical epoxy equivalent of the derivative. Up to 1 · 1 times. The ionic halogen content is 10 PP m or less, and it forms a transparent liquid when melted. When it is stored at χ 50 ° C for 24 hours, the epoxy equivalent increases by up to 3%. The method includes steps (A) to (D): Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (A) Epihalohydrin or 2-methyl-epihalohydrin is reacted with a compound having 2 to 4 carboxyl groups or 1 to 3 amido groups in the molecule. Containing the compound and the epihalohydrin or 2-methyl-epihalohydrin in a ratio of 1 mole of the compound's active hydrogen atom of the carboxyl or amido group to 1.2 to 60 mole of epihalohydrin or 2-methyl -Epihalohydrin, and a catalytically effective amount of a tertiary amine, a quaternary ammonium base or salt, a trisubstituted phosphine or a quaternary scale salt, thus forming a 2-hydroxy-3 propyl derivative or 2-hydroxy group containing the compound A 2-methyl-3-halopropyl derivative, (B) an alkali metal hydroxide is gradually added to the reaction product at a ratio of 1 to 2 moles of hydroxide to 1 mole of step (A) The active hydrogen atom of the carboxyl group or amido group of the compound in the previous reaction product, in order to trigger this paper, applicable to China CNS A4 specification (210X297 mm) -1 487697 A8 B8 C8 D8 month mouth sa ip, Shenchong VI, applied for patent scope and completed dehydrohalogenation of the derivative. Stirring formed contains precipitate Alkali metal halide slurry, thus forming a compound containing the compound 2'3-epoxypropyl derivative or 2-methyl-2'3-epoxypropyl derivative 'and the alkali metal halide produced by dehydrohalogenation The final slurry, (C) is a sulfonic acid, a sulfonate, a carboxylic acid having at least 7 carbon atoms in the molecule, a sulfate ester of an alcohol having at least 4 carbon atoms in the molecule, or a mixture thereof in water at 30 ° C The solubility is at least 1% by weight. As an aqueous solution of the refined preparation, the final slurry prepared in the cleaning step (B) or a liquid product prepared by removing the alkali metal halide from the final slurry in the step (B). The content can effectively refine the slurry or liquid product, thus forming a refined liquid containing the derivative formed in step (B), and (D) removing the epihalohydrin in the refined liquid obtained in step (C) or 2— Methyl-table Alcohol, thus forming the purification of the compound 2,3-epoxypropyl derivative or 2-methyl-2,3-epoxypropyl derivative (please read the precautions on the back before filling this page), 11 Economic Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau. 2 · According to item 1 of the scope of the patent application, the method is to perform step (B) in a container with a hydroxide concentration of 20 to 7 Ow t%, and maintain the slurry in a stirred state. It makes the slurry rise from the bottom along the inner wall of the container to the surface of the slurry, the vortex flows downward, and cuts the vortex, so that the water steamed from the slurry in a vacuum at a temperature of 10 to 80 ° C . Biological method, which includes adding an aqueous hydroxide solution to generate a circulating flow, and the upwelling is converted into a slurry to keep it uniform, and it is removed or added. -F- This paper applies the Chinese National Standard (CNS) A4 specification (210X297). Mm) 1 2-487697 A8 ν.Λ ·· ^ ../; v.; _ 5 B8 t; TI C8 II C > ^. I D8 _: _ Fang Fang: 丨 VI. Application scope 3. The scope of application for the patent No. 1 method for producing derivatives, in which (please read the precautions on the back before filling this page) to perform step (C) cleaning the liquid product by a method, which includes the average particle diameter of 0. 1 to 1 mm aqueous solution droplets are introduced into the column of the liquid product layer, so that the droplets rise, and then are combined in the column to form an aqueous layer, and the cycle in the column is gradually repeated, which consists of the introduction, ascent and combination of droplets And continue to supply the aqueous solution to the liquid product by introduction until the liquid product is introduced into the liquid product in an amount of 0. 0 to 0 1 to 5 parts by weight of the refined product relative to 100 parts by weight of the liquid product, such as The purified liquid product. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs4. The method of producing derivatives as described in item 1 of the scope of patent application, wherein the evaporation of step (D) is performed in a method that includes coating a refined liquid on the surface of a substrate The thickness of the membrane or its concentrated liquid is 30 to 500 / zm. The refined liquid at one end of the membrane or the concentrated liquid has the highest concentration of the volatile component. The concentration is gradually reduced until the refined liquid at the other end of the membrane or its concentration. The concentration of the volatile component in the liquid is the lowest, and the component is evaporated from the membrane at a pressure of 5 imn H g or below at 100 to 16 5 ° C, and the highest concentration of the volatile component in the membrane is at the same time. The refined liquid or its concentrated liquid is continuously supplied, and under evaporation and the thickness of the film is reduced, it is gradually transported toward the other end of the liquid, and the final liquid with a reduced concentration of volatile components is continuously recovered from the other end of the film. 5. The method for producing derivatives according to item 3 or 4 of the scope of patent application, wherein step (B) is performed in a container in a method that includes adding an alkali metal having a hydroxide concentration of 20 to 70 wt% Aqueous hydroxide solution, and maintain the slurry in a stirred state, which causes the slurry to circulate. The paper size is applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) -3-487697 A8 B8 C8 D8 VI. Application Patent scope ~~~~~~ — (Please read the precautions on the back before filling this page), rising from the bottom along the inner wall of the container to the surface of the slurry, and the rising flow turns into a vortex downward flow and cuts the Vortex, so that the slurry is kept 'evaporated from the slurry in a vacuum at 10 to 80 ° C to remove added or generated water. 6. The method for producing a derivative according to item 2 or 4 of the scope of patent application, wherein step (C) is used to clean the liquid product in a method that includes droplets of an aqueous solution having an average particle diameter of 0.1 to 1 Oirnn Into the column of the liquid product layer, the droplets are raised, and then combined in the column to form an aqueous layer. The cycle in the column is gradually repeated, which consists of the introduction, ascent and combination of droplets, and continuously introduces the The liquid product is supplied to the aqueous solution until 0.01 to 5 parts by weight of the refined product with respect to 100 parts by weight of the derivative product is introduced into the liquid product, and the liquid product is thus purified. 7. The method for producing derivatives as described in item 2 or 3 of the scope of patent application, wherein the evaporation of step (D) is performed by a method which includes coating a film of a refined liquid or a concentrated liquid thereof on a substrate surface, which The thickness is 30 to 500. Among the refined liquid or concentrated liquid at one end of the film, the concentration of the hair-printing component printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is the highest, and the concentration is gradually reduced until the liquid or the refined liquid at the other end of the film is refined. The concentration of the volatile component in the concentrated liquid is the lowest, and the component is evaporated from the film at a pressure of 100 to 16 5 ° C under the pressure of 5 legs H g or below, and the concentration of the volatile component of the film is the highest. The refined liquid or its concentrated liquid is continuously supplied at one end, and is gradually transported toward the other end of the liquid under evaporation and the thickness of the film is reduced, and the final liquid with a reduced concentration of volatile components is continuously recovered from the other end of the film. This paper size applies to Chinese National Standard (CNS) A4 specifications (210X297 male-4-487697 A8 B8 C8 D8 VI. Application for patent scope 8 · If the patent application scope No. 2 method of producing derivatives, which (Please read the back first (Notes to fill in this page again)) Perform step (C) to clean the liquid product in a method that includes introducing droplets of an aqueous solution having an average particle diameter of 0.1 to 10 nmi into a column of the liquid product layer, so that the The droplets rise, and then combine to form an aqueous solution layer in the column. The cycle in the column is repeated step by step, which consists of the introduction, ascent, and combination of the droplets, and the aqueous solution is continuously supplied to the liquid product by the introduction until it is relative to 1 0 0 parts by weight of the derivative of the liquid product, 0. 0 1 to 5 parts by weight of the refined product is introduced into the liquid product, so that the liquid product is refined, and the evaporation of step (D) is performed in a method, the The method includes coating a film of a refined liquid or a concentrated liquid on a substrate surface with a thickness of 30 to 50 0 // m. The highest concentration of sexual components, gradually reduce the concentration until the concentration of volatile components in the refined liquid or concentrated solution at the other end of the membrane is the lowest, and at a pressure of 5_Hg or below, from 100 to 16 5 ° C Ministry of Economic Affairs Printed by the Industrial Property Consumer Cooperative of the Intellectual Property Bureau. The component is evaporated from the film, and the refined liquid or its concentrated liquid is continuously supplied to the highest end of the volatile component concentration of the film. After evaporation and the thickness of the film decreases, gradually It is transported towards the other end of the liquid, and the final liquid with a reduced concentration of volatile components is continuously recovered from the other end of the membrane. 9 · The method for producing a derivative as described in the first patent application, wherein the reaction of step (A) is continued until 90% or more of the active hydrogen ions in the reaction product disappear. 10 · The method for producing a derivative as described in item 1 of the scope of patent application, wherein the refined preparation in step (C) is benzenesulfonic acid or toluenesulfonic acid, or Benzene sulfonic acid, toluene sulfonic acid, vinyl sulfonic acid salts, vinyl sulfonic acid polymers, and paper sizes are applicable to Chinese National Standard (CNS) A4 (210X297 mm) " -5-487697 A8 B8 C8 D8 6. Scope of patent application Polycondensate of sulfonic acid and formaldehyde, tetrahydrophthalic acid, lauryl sulfate, phthalic acid, salicylic acid or cinnamic acid. (Please read the notes on the back before filling this page) 1 1 · The method for producing derivatives according to item 1 of the scope of patent application, wherein the compound in step (A) is terephthalic acid, and the derivative in step (d) is terephthalic acid bis (2,3-epoxypropyl group) ) Ester or bis (2 ~ methyl-2,3-epoxypropyl) terephthalate. 1 2 · The method for producing derivatives as described in the first item of the patent application, wherein the compound in step (A) is Isocyanuric acid, the derivative in step (d) is tris (2,3-epoxypropyl) isocyanurate or tris (2-methyl-2,3-epoxypropyl) isocyanurate )ester. 1 3 · The method for producing derivatives as described in item 11 of the scope of patent application, wherein the following step (E) is added to produce a more purified product: (E) The product is formed by dissolving the product in a solvent as described in the application The solution of the product obtained in step (D) of item 11 of the patent scope, the derivative is precipitated from the solution in crystalline form, the solution is removed, and the precipitate is dried. 1 4 · The method of producing derivatives as described in item 12 of the scope of patent application, which includes the following step (E) to produce a more purified product. · Printed by the A Industrial Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (E) By dissolving the product in a solvent to form a solution of the product prepared in step (D) of item 11 of the patent application scope, the derivative is precipitated from the solution in crystalline form, the solution is removed, and the precipitate is dried. 15 · A method for preparing tri (2,3-epoxypropyl) isocyanurate or tri (2-methyl-2,3-epoxypropyl) isocyanurate, which is a purified product The epoxy equivalent is 1 · 0 to 1 · 1 times the theoretical epoxy equivalent of isocyanurate, which forms a transparent liquid when melted. This method covers the paper size and applies the Chinese National Standard (CNS) A4 specification (210X297 mm). ) 487697 A8 B8 C8 D8 3CU2,! Revise L 丨 supplement i 々, the scope of patent application includes steps (A) to (D): (Please read the precautions on the back before filling this page) (A): React epihalohydrin or 2-methyl-epihalohydrin with isocyanuric acid in a reaction mixture containing isocyanuric acid, the epihalohydrin or 2-methyl-epihalohydrin at a ratio of 1 mole Isocyanuric acid has an active hydrogen atom of 1.2 to 60 mol of epihalohydrin or 2-methyl-epihalohydrin, and an effective amount of tertiary amine printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. , A quaternary ammonium base or salt, a trisubstituted phosphine or a quaternary iron salt, thus forming an isocyanurate-containing tri (2-hydroxy-3-halopropyl) ester or Isocyanuric acid (2-hydroxy-1, 2-methyl-1, 3-halopropyl) ester, (B): In the reaction product in the container, the reaction product in step (A) before the reaction is performed every 1 mole. The active hydrogen atom of isocyanuric acid is gradually added to 1 to 2 moles, which is an aqueous solution of an alkali metal hydroxide having a concentration of 20 to 70 wt%, causing and completing the dehydrogenation of isocyanurate in the reaction product. Halogenation, forming a slurry containing the precipitated alkali metal halide, and maintaining the slurry in a stirred state, which causes the slurry to circulate, rising from the bottom along the inner wall of the container to the surface of the slurry, and the rising flow turns into a vortex here Downflow and shear the vortex to keep the slurry uniform. Evaporate and remove the added or generated water from the slurry in a vacuum at 10 to 80 ° C to form isocyanuric acid containing three (2, The final slurry of 3-epoxypropyl) ester or tris (2-methyl-2,3-epoxypropyl) isocyanurate and the alkali metal halide produced by the reaction, (C) washing step with water ( B) the final slurry or removal step (B) the liquid product of metal halide in the final slurry In this way, a refined liquid containing the isocyanurate is formed, and (D) the evaporation and removal table of the refined liquid prepared from step (C) _ Alcohol This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -7 — 487697 A8 month B8 C8 D8 VI. Scope of patent application ^ (Please read the notes on the back before filling this page) or 2-methyl-epihalohydrin, so isocyanuric acid tri (2,3 Monoglycidyl ester or tris (2-methyl-2,3-glycidoxy) isocyanurate, which is a purified product. 1 6 · —Method for preparing tris (2,3-epoxypropyl) isocyanurate or tris (2-methyl-2,3-epoxypropyl) isocyanurate The product has an epoxy equivalent of 1 · 0 to 1 · 1 times the theoretical epoxy equivalent of isocyanurate, which forms a transparent liquid when melted. The method includes steps (A) to (D): (A): make the table Halohydrin or 2-methyl-epihalohydrin reacts with isocyanuric acid in a reaction mixture containing isocyanuric acid, the epihalohydrin or 2-methyl-epihalohydrin at a ratio of 1 mole isocyanide The active hydrogen atom of uric acid is from 1.2 to 60 moles of epihalohydrin or 2-methyl-epihalohydrin, and a catalytically effective amount of a tertiary amine, a quaternary ammonium base or salt, a trisubstituted phosphine or Quaternary iron salt, thus forming the isocyanurate tris (2-hydroxy-3 -halopropyl) ester or isocyanurate tris (2-hydroxy-2-methyl-3halopropyl) ester, Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (B) The alkali metal hydroxide is gradually added to the reaction product at a ratio of 1 to 2 moles of hydroxide to 1 mole of the reaction product before step (A) in An active hydrogen atom of isocyanuric acid to initiate and complete the dehydrogenation of the derivative, stirring to form a slurry containing precipitated alkali metal halide, thus forming the isocyanuric acid containing tri (2,3-epoxy Propyl) ester or tris (2-methyl-2,3-epoxypropyl) isocyanurate, and the final slurry of the alkali metal halide produced by this reaction, (C) Step (B) The final size of the paper is determined by the Chinese National Standard (CNS) A4 (210 X 297 mm) -8 487697 A8 B8 6. The scope of the patent application for a liquid product prepared by removing alkali metal halides, the method includes introducing water droplets with an average particle diameter of 0.1 to 10 brain into a column of the liquid product layer to raise the droplets Then, it is combined in the column to form an aqueous solution layer, and the cycle in the column is repeated step by step, which consists of the introduction, ascent and combination of droplets, and continuously supplies water to the liquid product by introduction until it is relative to 100 parts by weight From 50 to 5000 parts by weight of the derivative product in the liquid product until water is introduced into the liquid product, an isocyanurate-containing purified liquid is thus formed. (D) Epihalohydrin or 2-methyl-epihalohydrin is removed by evaporation from the refined liquid obtained in step (C), so that tris (2,3-epoxypropyl) isocyanurate or isocyanurate is formed. Tris (2-methyl-2,3-epoxypropyl) acid, which is a purified product. 1 7 · A method for preparing tri (2,3-epoxypropyl) isocyanurate or tri (2-methyl-2,3-epoxypropyl) isocyanurate, which is purified The product has an epoxy equivalent of 1.0 to 1.1 times the theoretical epoxy equivalent of isocyanurate, which forms a transparent liquid when melted. The method includes steps (A) to (D): (A): make the table A halohydrin or 2-methyl-epihalohydrin is reacted with isocyanuric acid in a reaction mixture containing isocyanuric acid. The epihalohydrin or 2-methyl-epihalohydrin has a ratio of 1 mole of isocyanuric acid. The active hydrogen atom of adenylic acid is from 1.2 to 60 mol of epihalohydrin or 2-methyl-epihalohydrin, and a catalytically effective amount of a tertiary amine, a quaternary ammonium base or salt, a trisubstituted phosphine or tetra Grade iron salt, thus forming the isocyanurate tris (2-hydroxy-3-halopropyl) ester or isocyanuric acid (2-hydroxy-2-methyl-3-halopropyl) ester Applicable to China National Standard (CNS) A4 specification (21〇 < 297mm) ~ -9 I (Please read the precautions on the back before filling this page), π • Γ Intellectual Property Bureau, Ministry of Economic Affairs, Industrial and Commercial Cooperatives Printed 48 7697 A8 B8 C8 D8 6. Scope of patent application, (Please read the notes on the back before filling this page) (B) Add alkali metal hydroxide to the reaction product gradually, the ratio is 1 to 2 moles of hydroxide The active hydrogen atom of the isocyanuric acid in the reaction product before the reaction with 1 mol step (A) was initiated to complete and complete the dehydrohalogenation of the derivative. The slurry containing the precipitated alkali metal halide was formed by stirring, Forms containing the tris (2,3-epoxypropyl) isocyanurate or tris (2-methyl-2,3-epoxypropyl) isocyanurate and the alkali metal halide generated by the reaction (C) the liquid product obtained by removing alkali metal halide from step (B) the final slurry by washing with water, so as to form a refined liquid containing isocyanurate, and consumed by the staff of the Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative printing (D) The epihalohydrin or 2-methyl-epihalohydrin is removed from the refined liquid prepared in step (C) by a method comprising coating a surface of a substrate with the refined liquid or a concentrate thereof. Film with a thickness of 30 to 5 0 0 // m Make the concentration of the volatile component in the refined liquid at one end of the membrane or its concentrated liquid the highest, and gradually reduce the concentration until the concentration of the volatile component in the refined liquid at the other end of the membrane or its concentrated liquid is the lowest, and be 5 mra H g or less Under the pressure, the volatile component is evaporated from the film at 100 to 165 ° C, and at the same time the refined liquid or its concentrated liquid is continuously supplied to the highest end of the volatile component concentration of the film. As the film thickness decreases, it is gradually transported towards the other end of the liquid, and the final liquid with a reduced concentration of volatile components is continuously recovered from the other end of the film, so that tris (2,3-epoxypropyl) isocyanate is formed or Tris (2-methyl-2,3-epoxypropyl) isocyanate, which is a purified product. This paper size applies to Chinese National Standards (CNS) A4 specifications (210X297 mm)-10-487697 sa la 12 A8 B8 C8 D8 6. Scope of patent application (please read the precautions on the back before filling this page) 1 8 · If Method for manufacturing tris (2'3-epoxypropyl) isocyanate or tris (2-methyl-2,3-epoxypropyl) isocyanate, in which the scope of application for patent is 15 The liquid product cleaning of step (C) is performed in a method including introducing water droplets having an average particle diameter of 0.1 to 10 mra into a column of the liquid product layer, causing the droplets to rise ', and then binding to An aqueous solution layer is formed in the column, and the circulation in the column is repeated step by step, which consists of the introduction, ascent, and combination of droplets, and continuously supplies water to the liquid product by the introduction effect until it is in the amount of 100 parts by weight of the liquid product. From 50 to 5000 parts by weight of the derivative, the refined product is introduced into the liquid product, thus forming a refined liquid containing isocyanurate. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Industrial Cooperative Cooperative, 19 · If the scope of patent application is No. 15, 16, or 18, the manufacture of isocyanuric acid tris (2,3-epoxypropyl) ester or isocyanuric acid Method for tris (2-methyl-2,3-epoxypropyl) ester, wherein the evaporation of step (D) is performed in a method, which comprises coating a film of a refined liquid or a concentrated liquid thereof on a substrate surface , Its thickness is 30 to 500 / zm, so that the concentration of the volatile component in the refined liquid or concentrated liquid at one end of the membrane is the highest, and gradually reduce the concentration until the volatile group in the refined liquid or concentrated liquid at the other end of the membrane The component concentration is the lowest, and the volatile component is evaporated from the film at a temperature of 100 to 16 5 ° C at a pressure of 5 min H g or less, and the highest end of the film volatile component concentration is continuously supplied. The liquid or its concentrate should be refined, and under evaporation and the thickness of the film is reduced, it is gradually transported towards the other end of the liquid, and the final liquid with a reduced concentration of volatile components is continuously recovered from the other end of the film, so that isocyanate is formed Tris (2,3-epoxypropyl) ester or tris (2— A 2,3-epoxypropyl) ester, which is a purified product. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -11-487697 A8 male & B8 C8 D8 6 Scope of patent application 0 (Please read the precautions on the back before filling out this page) 2 0 · If you apply for any of the patent scope 15 to 18 to manufacture isocyanuric acid tri (2,3-epoxy A method of propyl) ester or tris (2-methyl-2,3-epoxypropyl) isocyanurate, wherein the following step (E) is added: (E) by dissolving the product in a solvent A solution of the product obtained in step (D) is formed in the step, the derivative is precipitated from the solution in a crystalline form, the solution is removed, and the precipitate is dried, thus forming a more purified product than in step (D). 21 · —A method for producing bis (2,3-epoxypropyl) terephthalate or bis (2-methyl-2,3-epoxypropyl) terephthalate, which is a purified product, a ring The oxygen equivalent is 1.0 to 1.1 times the theoretical epoxy equivalent of terephthalate, which forms a transparent liquid when melted. The method includes steps (A) to (D): (A): making epihalohydrin or 2 -Methyl-epihalohydrin reacts with terephthalic acid in a reaction mixture containing terephthalic acid, the epihalohydrin or 2-methyl-epihalohydrin in a ratio of 1 mole of active hydrogen atom to the phthalic acid 1.2 printed to 60 moles of epihalohydrin or 2-methyl-epihalohydrin, and catalytically effective amounts of tertiary amines, quaternary ammonium bases or salts, tris Substituted phosphine or quaternary scale salt to form bis (2-hydroxy-3 -halopropyl) terephthalate or bis (2-hydroxy-1 2-methyl-3-halopropyl) terephthalate (B): In the reaction product in the container, step (A) is performed every 1 mole of the terephthalic acid active hydrogen atom contained in the reaction product before the reaction, gradually adding 1 to 2 moles, which is the concentration It is 20 to 7 Ow t% alkali metal. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) ~ ~ 12- 487697 申请, the scope of patent application for hydroxide aqueous solution, leading to and complete the dehydrohalogenation of the phthalic acid ester in the reaction product, forming a slurry containing the precipitated alkali metal halide, and maintaining the slurry in a stirred state, which makes the slurry A circulating flow is generated, rising from the bottom along the inner wall of the container to the surface of the slurry, where the rising flow turns into a vortex downward flow and shears the vortex flow, so that the slurry is kept uniform, in a vacuum from 10 to 80 At a temperature of ° C, the added or generated water is removed by evaporation from the slurry to form bis (2,3-epoxypropyl) terephthalate or bis (2-methyl-2,3-epoxypropyl) terephthalate. ) The final slurry of the alkali metal halide produced by the ester and the reaction, (C) washing the final slurry of step (B) with water or removing the liquid product of the alkali metal halide in the final slurry (B), thus forming the Ester refined liquid and (D) the refined liquid prepared from step CC) is evaporated to remove epihalohydrin or 2-methyl-epihalohydrin, thus forming isocyanuric acid tri (2,3-epoxypropyl group) ) Ester or isocyanurate tri (2 — A group 2,3 - epoxypropyl) isocyanurate as a purified product. 22 · A method for preparing bis (2,3-epoxypropyl) terephthalate or bis (2-methyl-2,3-epoxypropyl) terephthalate, which is a purified product, ring The oxygen equivalent is 1 · 0 to 1 · 1 times the theoretical epoxy equivalent of terephthalate, which forms a transparent liquid when melted. The method includes steps (A) to (D): (A): making epihalohydrin or 2 —Methyl-epihalohydrin reacts with terephthalic acid in a reaction mixture containing terephthalic acid, the epihalohydrin or 2-methyl-epihalohydrin in a ratio of 1 mole of active hydrogen atom pair of phthalic acid 1 · 2 to this paper size apply Chinese National Standard (CNS) A4 specification (210X297mm);-, ------ (Please read the precautions on the back before filling this page) Order f Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives -13-487697 A8 B8 C8 D8 1 Da'Zhengliu Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. Application for a patent scope 60 0 Mol of epihalohydrin or 2-methyl-epihalide Alcohol, and a catalytically effective amount of a tertiary amine, a quaternary ammonium base or salt, a trisubstituted phosphine or a quaternary iron salt, thus forming a bis (2-hydroxy A 3-halopropyl) ester or bis (2-hydroxy-2-methyl-3-halopropyl) terephthalate, (B) The alkali metal hydroxide is gradually added to the reaction product, and the ratio is 1 to 2 moles of hydroxide to 1 mole of the active hydrogen atom of the p-phthalic acid in the reaction product before the reaction in step (A) to initiate and complete the dehydrohalogenation of the derivative. Metal halide slurry, so as to contain the bis (2,3-epoxypropylΓ) terephthalate or bis (2-methyl-2,3-epoxypropyl) terephthalate, and the reaction produces The final slurry of the alkali metal compound, (C) The liquid product prepared by removing the alkali metal halide from the final slurry of step (B) with water in a method, the method including the average particle diameter of 0.1 to 1 The 0-leg water droplet is introduced into the column of the liquid product layer, so that the droplet rises, and then combines in the column to form an aqueous layer. The cycle in the column is gradually repeated, which consists of the introduction, ascent and combination of droplets, and The liquid product is continuously supplied with water by introduction until it is relative to 1 0 0 50 to 500 parts by weight of the weight of the derivative in the liquid product until the water is introduced into the liquid product, so that a purified liquid containing terephthalate is formed. (D) Prepared from step (C) The refined liquid is evaporated to remove epihalohydrin or 2-methyl-epihalohydrin, thus forming bis (2,3-epoxypropyl) terephthalate or bis (2-methyl-2,3-cyclophthalate) Oxypropyl) ester, which is a purified product. This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) Ί 丨 ^-(Please read the precautions on the back before filling this page) Order f- 14-487697 A8 B8 C8 D8 々 、 Scope of patent application (please read the precautions on the back before filling in this page) 2 3 · — Preparation of bis (2,3 —epoxypropyl) terephthalate or terephthalic acid A method of bis (2-methyl_2,3-epoxypropyl) ester, which is a purified product, the epoxy equivalent is isocyanurate theoretical epoxy equivalent i. 0 to 1.1 times' in the melt When a transparent liquid is formed, the method includes steps (A) to (D): (A) • bringing epidentate or 2-methyl-epidentitol to The isocyanuric acid in the reaction mixture reacts, the epihalohydrin or 2-methyl-epihalohydrin 'in a ratio of 1 mole of terephthalic acid to active hydrogen atoms to 1.2 to 60 moles of epihalohydrin Or 2-methyl-epihalohydrin, and a catalytically effective amount of a tertiary amine, a quaternary ammonium base or salt, a trisubstituted phosphine, or a quaternary scale salt, so that the bis (2-hydroxy-3) -Halopropyl) ester or bis (2-hydroxy-2-methyl-1,3-halopropyl) terephthalate, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (B) and gradually add a base to the reaction product Metal hydroxide in a ratio of 1 to 2 moles of hydroxide to 1 mole of the active hydrogen atom of the paraphthalic acid in the reaction product before the reaction in step (A) to initiate and complete dehydrohalogenation of the derivative Effect, stirring to form a slurry containing precipitated alkali metal halide, thus forming the bis (2,3-epoxypropyl) phthalate or bis (2-methyl-2,3-epoxy) (Propyl) ester, and the final slurry of the alkali metal halide produced by the reaction, (C) washing with water to remove the alkali metal from the final slurry of step (B) The liquid product prepared from the compound, thus forming a purified liquid containing terephthalate, and (D) removing the epihalohydrin or 2-methyl-epihalohydrin from the purified liquid obtained in step (C) in a manner This method includes applying the Chinese National Standard (CNS) A4 specification (210X297 mm) to the paper size on a substrate surface. 15-487697 90.12. 1 Z A8 B8 C8 D8. 6. Application scope of patents (please read the precautions on the back first) (Fill in this page again) Apply a film of refined liquid or its concentrate to a thickness of 30 to 5 00 am to maximize the concentration of the volatile component in the refined liquid or its concentrate at one end of the film, and gradually reduce the concentration until The concentration of volatile components in the refined liquid or its concentrated liquid at the other end of the membrane is the lowest, and the volatile components are evaporated from the membrane at a pressure of 5 mm H g or below at 100 to 16 5 ° C. At the same time, the refined liquid or its concentrated liquid is continuously supplied to the highest end of the volatile component concentration of the membrane, and it is gradually transported towards the other end of the liquid under evaporation and the thickness of the membrane is reduced, and the volatilization is continuously recovered from the other end of the membrane Sexual component Reducing the final liquid, thus forming terephthalic acid bis (2,3 - epoxypropyl) ester or terephthalic acid bis (2,3-methyl 2_ - epoxypropyl) isocyanurate as a purified product. 24. The method for manufacturing bis (2,3-epoxypropyl) terephthalate or bis (2-methyl-2,3-epoxypropyl) terephthalate according to item 21 of the patent application, wherein The evaporation of step (D) is performed by a method including introducing droplets printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Water Economics and the Intellectual Property Bureau of the Ministry of Water Economy into a column of the liquid product layer with an average particle diameter of 0.1 to 10, The droplet is raised, and then combined in the column to form an aqueous layer. The cycle in the column is gradually repeated, which consists of the introduction, ascent and combination of droplets, and continuously supplies water to the liquid product by introduction until From 50 to 500 parts by weight of the derivative in the 100 parts by weight of the liquid product until water is introduced into the liquid product, a purified liquid containing terephthalate is thus formed. 25 · Manufacture of bis (2,3-epoxypropyl) terephthalate or bis (2-methyl-2,3-epoxypropyl) terephthalate, as in the scope of application for patent No. 21, 22 or 24 Method, in which the steps are carried out in one method. The dimensions of this sheet are in accordance with the Chinese National Standard (CNS) A4 specifications (210X297 mm 1-16-487697 A8 B8 C8 D8. 6. Scope of patent application (please read the notes on the back before filling in (This page) (D) evaporation method, the method includes coating a film of refined liquid or its concentrated liquid on a substrate surface, the thickness of which is 30 to 50 0 // m The concentration of the volatile component in the liquid is the highest, and gradually reduce the concentration until the concentration of the volatile component in the refined liquid or the concentrated liquid at the other end of the membrane is the lowest, and at a pressure of 5 mm H g or less, from 100 to At 16 ° C, the volatile component is evaporated from the film. At the same time, the refined liquid or its concentrated liquid is continuously supplied to the highest end of the volatile component of the film. After evaporation and the thickness of the film decreases, it gradually moves towards the The other end of the liquid is transported and continuously returned from the other end of the membrane The final liquid with a reduced concentration of volatile components, thus forming tris (2,3-epoxypropyl) isocyanate or tris (2-methyl-2,3-epoxypropyl) isocyanate, which It is a purified product. 2 6 · Manufacturing bis (2,3-epoxypropyl) terephthalate or bis (2-methyl-1) terephthalate as in any one of claims 21 to 24 The method of 2,3-epoxypropyl) ester, in which the following steps (E) are added: (E) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, forming the step (d) by dissolving the product in a solvent A solution of the product is obtained, and the derivative is precipitated from the solution in a crystalline form, and the solution is removed, and the precipitate is dried, so as to form a product that is more pure than step (D). This paper size applies to Chinese national standards ( CNS) A4 size (210X297 mm)-17-