A method for preparing epoxy compound

Abstract

The present invention provides a method for preparing an epoxy compound, comprising: an oxidative reaction of a triene isotrimer acid ester compound with hydrogen peroxide under the action of a catalyst, an auxiliary catalyst and a salt to obtain a triglycidyl isocyanate compound. The present invention uses hydrogen peroxide as an oxidant, and under the action of a catalyst, an auxiliary catalyst and a salt, the target product is obtained efficiently, safely and with high quality, and the reaction conditions are mild, the process is simple, the reaction time is short, and the compound has the advantages of being green, environmentally friendly and low in cost.

Description

Technical Field

[0001] The present invention relates to the technical field of epoxy compound synthesis, and in particular to a method for preparing an epoxy compound. Background Art

[0002] Crystalline epoxy resins have high heat resistance due to their rigid main chain skeleton or multi-functional groups, and are used in fields that require heat resistance and reliability, such as the electrical and electronic fields. Crystalline epoxy resins are limited to applications using solid materials such as transfer molding, so their scope of use is limited; in addition, the epoxy resins used in liquid molding such as cast molding are liquid epoxy resins, which cannot fully meet the requirements for improved curing properties such as heat resistance in the fields of bonding, casting, sealing, molding, lamination, etc., which require stricter requirements. Among them, triglycidyl isocyanate is a typical representative as a curing agent for carboxyl functional resin powder coatings. High-purity TGIC (triglycidyl isocyanurate) also has excellent high-temperature electrical properties and can be used to manufacture electrical insulation materials and printed circuits; it can also be used in laminates and plastic stabilizers; due to its good weather resistance, high thermal stability, and superior mechanical properties, it has a wide range of uses.

[0003] At present, in the preparation process of triglycidyl isocyanate, there is a method for synthesizing triglycidyl isocyanurate using isocyanuric acid and epichlorohydrin as raw materials and water as a co-solvent; there is also a method such as Chinese invention patent application CN201611157829.8, which uses sodium cyanate as a raw material and prepares triglycidyl isocyanurate through substitution and condensation reactions. It includes the following steps: sodium cyanate, epichlorohydrin, benzyl bromide organic catalyst, 30% hydrogen peroxide, and polar solvent are mixed into a reactor at one time according to proportion, stirred at room temperature for 10 minutes, heated to control the temperature at 70-90°C, and refluxed for 3-5 hours before post-treatment to obtain triglycidyl isocyanurate.

[0004] The traditional process uses epichlorohydrin as the main raw material, which produces a large amount of wastewater and waste salt. At the same time, the reaction produces a variety of by-products, especially by-products containing organic chlorine, which are difficult to separate from the product and have high product refining costs. At the same time, the cost of this process is greatly affected by the price fluctuations of epichlorohydrin, which is not conducive to market stability and corporate development. Therefore, it is necessary to develop new technical processes to reduce environmental pollution while improving product yield and quality, and at the same time achieve process breakthroughs for high-end electronic-grade products. Summary of the invention

[0005] In view of the defects in the prior art, the object of the present invention is to provide a method for preparing an epoxy compound.

[0006] According to one aspect of the present invention, there is provided a method for preparing an epoxy compound, the method comprising: an oxidative reaction of a triene isotrimer acid ester compound I with hydrogen peroxide in the presence of a catalyst, an auxiliary catalyst and a salt to obtain a triglycidyl isocyanate compound II;

[0007] The structural formulas of triolefin isotrimer ester compound I and triglycidyl isocyanate compound II are as follows:

[0008]

[0009] Wherein, R in (I) is a methyl group or a hydrogen atom, n1 、 n2 、 n3 is any integer from 1 to 3; R in (II) is a methyl group or a hydrogen atom, n1 、 n2 、 n3 is any integer from 1 to 3.

[0010] Optionally, the molar ratio of the triene isotrimer acid ester compound I to hydrogen peroxide is: 1:(3-5), and the concentration of hydrogen peroxide is 5%-50%.

[0011] Optionally, the molar ratio of the triene isotrimer acid ester compound I to the catalyst is 1:(0.001-0.5).

[0012] Optionally, the molar ratio of the triene isotrimer acid ester compound I to the auxiliary catalyst is 1:(0.001-0.5).

[0013] Optionally, the molar ratio of the triene isotrimer acid ester compound I to the salt is 1:(0.001-1).

[0014] Optionally, the reaction temperature of the oxidation reaction is -10 to 100°C; and the reaction time is 30s to 10h.

[0015] Optionally, the solvent is any one or more of methanol, ethanol, isopropanol, DMF, NMP, ethyl acetate, acetonitrile, THF, methyl tert-butyl ether, acetone, water, toluene, dichloromethane, chloroform, dichloromethane, and dioxane.

[0016] Optionally, the catalyst is any one or more of organic aliphatic amines, aromatic amines, nicotinic acid, substituted nicotinic acid, amino alcohols, amino acids, glycine, DMAP, DABCO, DBU, pyrazole compounds, imidazole compounds, pyridazine and its derivatives, and pyrazine and its derivatives.

[0017] Optionally, the auxiliary catalyst is any one of phosphate, carbonate, sulfate, acetate, tungstate, molybdate, phosphomolybdate, phosphotungstate, manganese acetate, manganese sulfate, cerium nitrate, lanthanum nitrate, vanadium oxide, and alkali metal hydroxide.

[0018] Optionally, the salt is any one or more of the following: a mixture of phosphate and hydrogen phosphate, a mixture of carbonate and hydrogen carbonate, acetate, formates, oxalates, aromatic salts, sulfates, hydrogen sulfates, and sulfonates.

[0019] Compared with the prior art, the present invention has at least one of the following beneficial effects:

[0020] 1. The preparation method of the epoxy compound of the present invention uses hydrogen peroxide as an oxidant, and obtains the target product efficiently, safely and with high quality under the catalysis of an efficient catalytic system formed by a catalyst, an auxiliary catalyst and a salt. The present invention provides a new process for preparing a large class of compounds with a structure similar to triglycidyl isocyanurate, which has mild reaction conditions, simple process and short reaction time, and has the advantages of being green, environmentally friendly and low cost.

[0021] 2. Compared with the traditional process, the present invention uses green and environmentally friendly hydrogen peroxide as the oxidizing agent, and the byproduct of the reaction is water; at the same time, the catalytic system can be recycled; the reaction solvent can be recovered and can be reused repeatedly without refining. In the case of adopting a multi-channel-continuous flow process, the efficiency and yield of the reaction can achieve a huge breakthrough: the process time is shortened from the traditional 4-6 hours to a fast completion within 30s-10min, and the yield can be increased to 95%. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Other features, objects and advantages of the present invention will become more apparent from the detailed description of non-limiting embodiments made with reference to the following drawings:

[0023] Figure 1 The structural formula of the triene isotrimer ester compound I and the triglycidyl isocyanate compound II in the embodiment of the present invention;

[0024] Figure 2 It is the reaction formula of the preparation method of the epoxy compound in the embodiment of the present invention. DETAILED DESCRIPTION

[0025] The present invention is described in detail below in conjunction with specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, several variations and improvements may be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

[0026] An embodiment of the present invention provides a method for preparing an epoxy compound, the method comprising:

[0027] The triolefin isotrimer acid ester compound I undergoes an oxidation reaction with hydrogen peroxide under the action of a catalyst, an auxiliary catalyst and a salt to obtain a triglycidyl isocyanate compound II;

[0028] The structural formulas of triolefin isotrimer ester compound I and triglycidyl isocyanate compound II are as follows: Figure 1 As shown, wherein R in (I) is a methyl group or a hydrogen atom, n1 、 n2 、 n3 is any integer from 1 to 3; R in (II) is a methyl group or a hydrogen atom, n1 、 n2 、 n3 is any integer from 1 to 3. The reaction formula of this reaction is as follows Figure 2 As shown, the by-product of the reaction is water, which will not pollute the environment and is green and environmentally friendly.

[0029] In some embodiments, the molar ratio of the triene isotrimer acid ester compound I to hydrogen peroxide is 1:(3-5). The concentration of hydrogen peroxide is 5%-50%, preferably 30%.

[0030] In some embodiments, the molar ratio of the triene isotrimer ester compound I to the catalyst is 1:(0.001-0.5), preferably, the molar ratio of the triene isotrimer ester compound I to the catalyst is 1:0.005. The embodiment of the present invention only requires a small amount of catalyst, and the catalytic system is highly efficient.

[0031] In some embodiments, the molar ratio of the triene isotrimer acid ester compound I to the auxiliary catalyst is 1:(0.001-0.5), preferably, the molar ratio of the triene isotrimer acid ester compound I to the auxiliary catalyst is 1:0.002.

[0032] In some embodiments, the molar ratio of the triene isotrimer acid ester compound I to the salt is 1:(0.001-1), preferably, the molar ratio of the triene isotrimer acid ester compound I to the salt is 1:0.01. Salt plays an important role in regulating the activity of the catalytic system. Without or in excess, the catalytic activity and efficiency will decrease significantly.

[0033] In some embodiments, the reaction temperature of the oxidation reaction is -10 to 100°C, preferably, the reaction temperature is -10 to 60°C; more preferably, 0 to 40°C; the reaction time is 30s to 10h, preferably, the reaction time is 30s to 0.5h, more preferably, the reaction time is 30s-10min.

[0034] In some embodiments, the solvent is any one or more of methanol, ethanol, isopropanol, DMF, NMP, ethyl acetate, acetonitrile, THF, methyl tert-butyl ether, acetone, water, toluene, dichloromethane, chloroform, dichloromethane, and dioxane. Preferably, the solvent is ethanol or toluene, ethanol is conducive to mixing with hydrogen peroxide, and toluene is conducive to dissolving the raw material.

[0035] In some embodiments, the catalyst is any one or more of organic aliphatic amines, aromatic amines, nicotinic acid, substituted nicotinic acid, amino alcohols, amino acids, glycine, DMAP, DABCO, DBU, pyrazole compounds, imidazole compounds, pyridazine and its derivatives, pyrazine and its derivatives. Preferably, the catalyst is nicotinic acid and its derivatives.

[0036] In some embodiments, the auxiliary catalyst is any one of phosphate, carbonate, sulfate, acetate, tungstate, molybdate, phosphomolybdate, phosphotungstate, manganese acetate, manganese sulfate, cerium nitrate, lanthanum nitrate, vanadium oxide, and alkali metal hydroxide. Preferably, the auxiliary catalyst is sodium phosphomolybdate or acetate.

[0037] In some embodiments, the salt is any one or more of the following: a mixture of phosphate and hydrogen phosphate, a mixture of carbonate and hydrogen carbonate, acetate, formates, oxalates, aromatic salts, sulfates, hydrogen sulfates, and sulfonates; preferably, phosphates are used.

[0038] In some embodiments, the preparation process of the epoxy compound further comprises the step of recrystallizing the crude product obtained by the reaction, and the recrystallization temperature is 10-100° C. The solvent selected for recrystallization includes ethanol, methanol, isopropanol, toluene, acetone, ethyl acetate, dichloromethane, chloroform, methyl tert-butyl ether, isopropyl ether, ethyl ether, petroleum ether, cyclopentane, cyclohexane, cycloheptane, n-pentane, n-hexane and n-heptane. Preferably, the solvent selected for recrystallization is ethanol, and the recrystallization temperature is 60° C.

[0039] The existing preparation method that does not use continuous flow can achieve a yield of 90%, but the entire process reaction time requires 4-6 hours. The preparation method of the epoxy compound in the above embodiment has the advantages of mild reaction conditions, simple process, short reaction time and low cost under traditional process conditions, and the yield exceeds 90%; the reaction can adopt both traditional kettle process and new multi-channel-continuous flow process. As a new process for preparing TGIC by hydrogen peroxide method using microchannel reaction equipment, it has achieved a new process breakthrough with high efficiency, high yield and intrinsic safety, which is in line with the development trend of green chemistry. The advantages of the preparation method of the present invention are mainly reflected in the following aspects:

[0040] 1. With hydrogen peroxide as the oxidant, under the catalysis of the high-efficiency catalytic system formed by the catalyst, auxiliary catalyst and salt, the double bond epoxidation efficiency is greatly improved, and the product yield and quality are greatly improved, and the comprehensive benefits are better than the traditional epichlorohydrin process;

[0041] 2. It can avoid the side reaction of epoxy ring opening in the epichlorohydrin process and fundamentally reduce the "three wastes" and chlorine-containing organic matter;

[0042] 3. The epoxidation reaction and product separation have the advantage of simple operation;

[0043] 4. After adopting the microchannel continuous flow reaction, the epoxidation time is shortened to within a few minutes, which avoids side reactions and strengthens the mass transfer and heat transfer performance of the reaction. The hydrogen peroxide conversion rate is high, and the inherent safety of the reaction is achieved.

[0044] The present invention is described in detail below by way of examples. It is necessary to point out here that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the contents of the present invention above still belong to the scope of protection of the present invention.

[0045] Example 1

[0046] 3.0g (9.0mmol) 1,3,5-tri-(pentenyl)-isocyanurate, 0.03g (0.15mmol) sodium phosphomolybdate, 0.003g (0.024mmol) nicotinic acid, sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2) were dissolved in 20mL ethanol, stirred, the system temperature was 20°C, and then 6ml of 30% hydrogen peroxide solution was slowly added to the ethanol solution, and the addition was completed in 3 hours, and the reaction was continued for another 3 hours. After the reaction was completed, the reaction solution was analyzed by GC (gas chromatography), and the raw material conversion rate was 98%. Finally, the reaction solution was filtered, and the filtrate was analyzed by HPLC (high performance liquid chromatography), confirming that the HPLC (high performance liquid chromatography) yield of 1,3,5-tri-(4,5-epoxypentyl)-isocyanurate was 91%.

[0047] Example 2

[0048] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.3g (0.015mmol) sodium phosphomolybdate, 0.002g (0.024mmol) nicotinic acid, sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2) were dissolved in 20mL ethanol, stirred, the system temperature was 20°C, and then 6ml of 30% hydrogen peroxide solution was slowly added to the ethanol solution, and the addition was completed in 3 hours, and the reaction was continued for another 3 hours. After the reaction was completed, the reaction solution was analyzed by GC (gas chromatography), and the raw material conversion rate was 99%. The reaction solution was filtered, and the filtrate was analyzed by HPLC (high performance liquid chromatography), confirming that the HPLC (high performance liquid chromatography) yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 94%.

[0049] Example 3

[0050] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.07mmol) sodium tungstate, 0.003g (0.024mmol) nicotinic acid, sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2) were dissolved in 20mL ethanol, stirred, the system temperature was 20°C, and then 6ml of 50% hydrogen peroxide solution was slowly added to the ethanol solution, and the addition was completed in 3 hours, and the reaction was continued for another 3 hours. After the reaction was completed, the reaction solution was analyzed by GC (gas chromatography), and the raw material conversion rate was 97%. The reaction solution was filtered, and the filtrate was analyzed by HPLC (high performance liquid chromatography), confirming that the HPLC (high performance liquid chromatography) yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 87%.

[0051] Example 4

[0052] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.015) sodium phosphomolybdate, 0.003g (0.024mmol) pyridine-2-carboxylic acid, sodium carbonate-sodium bicarbonate buffer solution (pH = 6.2) were dissolved in 20mL ethanol, stirred, the system temperature was 20°C, and then 6ml of 30% hydrogen peroxide solution was slowly added to the ethanol solution, and the addition was completed in 3 hours, and the reaction was continued for another 3 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 98%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 90%.

[0053] Example 5

[0054] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.18mmol) manganese acetate, 0.003g (0.024mmol) pyridine-2-carboxylic acid, sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2) were dissolved in 20mL ethanol, stirred, the system temperature was 20°C, 6ml 35% hydrogen peroxide solution was slowly added to the ethanol solution, the addition was completed in 3 hours, and the reaction was continued for another 3 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 98%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 91%.

[0055] Example 6

[0056] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.20mmol) manganese sulfate, 0.003g (0.024mmol) pyridine-2-carboxylic acid, sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2) were dissolved in 20mL ethanol, stirred, the system temperature was 20°C, and then 6ml of 40% hydrogen peroxide solution was slowly added to the ethanol solution, and the addition was completed in 3 hours, and the reaction was continued for another 3 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 98%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 91%.

[0057] Example 7

[0058] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.015mmol) sodium phosphomolybdate, 0.003g (0.027mmol) DABCO (triethylenediamine), sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2) were dissolved in 20mL ethanol, stirred, the system temperature was 20°C, and then 40ml of 5% hydrogen peroxide solution was slowly added to the ethanol solution, and the addition was completed in 3 hours, and the reaction was continued for 2 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 98%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 81%.

[0059] Example 8

[0060] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.015mmol) sodium phosphomolybdate, 0.003g (0.034mmol) 1,3,5-triazine, sodium oxalate-sodium dihydrogen phosphate buffer solution (pH = 6.2) were dissolved in 20mL ethanol, stirred, the system temperature was 20°C, 6ml 30% hydrogen peroxide solution was slowly added to the ethanol solution, the addition was completed in 3 hours, and the reaction was continued for 2 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 99%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 81%.

[0061] Example 9

[0062] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.01mmol) sodium phosphotungstate, 0.003g (0.024mmol) pyridine-2-carboxylic acid, sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2) were dissolved in 20mL ethanol, stirred, the system temperature was 20°C, and then 6ml of 30% hydrogen peroxide solution was slowly added to the ethanol solution, and the addition was completed in 3 hours, and the reaction was continued for another 3 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 99%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 95%.

[0063] Example 10

[0064] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.01mmol) sodium phosphotungstate, 0.003g (0.05mmol) ethanolamine, sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2), dissolved in 20mL ethanol, stirred, the system temperature was 20°C, and then 6ml of 30% hydrogen peroxide solution was slowly added to the ethanol solution, and the addition was completed in 3 hours, and the reaction was continued for another 3 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 98%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 83%.

[0065] Embodiment 11

[0066] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.01mmol) manganese chloride, 0.003g (0.027mmol) DABCO, sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2), dissolved in 20mL ethanol, stirred, the system temperature was 20°C, and then 6ml 30% hydrogen peroxide solution was slowly added to the ethanol solution, and the addition was completed in 3 hours, and the reaction was continued for another 3 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 98%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 86%.

[0067] Example 12

[0068] 4.48g (18mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.27g (18mmol) sodium tungstate, 0.21g (18mmol) nicotinic acid, sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2) were dissolved in 100mL methanol / acetone, stirred, the system temperature was 20°C, 12ml 30% hydrogen peroxide solution was slowly added to the solution, the addition was completed in 3 hours, and the reaction was continued for 10min. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 99%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 92%.

[0069] Example 13

[0070] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.01mmol) sodium phosphotungstate, 0.003g (0.024mmol) pyridine-2-carboxylic acid, sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2) were dissolved in 20mL acetonitrile, stirred, the system temperature was 20°C, and then 6ml of 30% hydrogen peroxide solution was slowly added to the acetonitrile solution, and the addition was completed in 3 hours, and the reaction was continued for another 3 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 98%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 87%.

[0071] Embodiment 14

[0072] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.01mmol) sodium phosphotungstate, 0.003g (0.04mmol) glycine, sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2) were dissolved in 20mL methanol, stirred, the system temperature was 20°C, and then 6ml of 30% hydrogen peroxide solution was slowly added to the methanol solution, and the addition was completed in 3 hours, and the reaction was continued for another 3 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 99%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 86%.

[0073] Embodiment 15

[0074] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.01mmol) sodium phosphotungstate, 0.003g (0.024mmol) pyridine-2-carboxylic acid, sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2) were dissolved in 20mL acetonitrile, stirred, the system temperature was 10°C, and then 6ml of 30% hydrogen peroxide solution was slowly added to the acetonitrile solution, and the addition was completed in 3 hours, and the reaction was continued for another 3 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 99%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 90%.

[0075] Example 16

[0076] 4.48g (18.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.06g (0.4mmol) manganese sulfate, 0.006g (0.048mmol) pyridine-2-carboxylic acid, sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2) were dissolved in 20mL acetonitrile, stirred, the system temperature was 10°C, and then 12ml 30% hydrogen peroxide solution was slowly added to the acetonitrile solution, and the addition was completed in 3 hours, and the reaction was continued for another 3 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 99%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 89%.

[0077] Embodiment 17

[0078] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.01mmol) sodium phosphotungstate, 0.03g (0.024mmol) pyridine-2-carboxylic acid, 1ml sodium carbonate-sodium sulfate solution, dissolved in 20mL DMF (N,N-dimethylformamide), stirred, the system temperature was 10°C, and then 6ml 30% hydrogen peroxide solution was slowly added to the DMF solution, and the addition was completed in 3 hours, and the reaction was continued for another 3 hours. The reaction solution was analyzed by GC, and the raw material conversion rate was 99%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 82%.

[0079] Embodiment 18

[0080] 5.30 g (9.0 mmol) of 1,3,5-tri-(10-undecenyl)-isocyanurate, 0.03 g (0.01 mmol) of sodium phosphomolybdate, 0.003 g (0.024 mmol) of nicotinic acid, and sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2) were dissolved in 20 mL of ethanol, stirred, and the system temperature was 20°C. 6 ml of 30% hydrogen peroxide solution was slowly added dropwise to the ethanol solution, and the addition was completed over 3 hours, and the reaction was continued for another 3 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 64%.

[0081] Embodiment 19

[0082] Dissolve 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.01mmol) sodium phosphotungstate, 0.003g (0.024mmol) pyridine-2-carboxylic acid in 20mL acetonitrile and stir; dissolve sodium phosphate-sodium dihydrogen phosphate buffer solution (pH=6.2) in 6ml 30% hydrogen peroxide solution, use double pumps for injection, one pump is used for injection of reaction substrate, solvent, catalyst, and the other pump is used for injection of hydrogen peroxide and salt; the injection flow rate ratio is 3.3:1, the reaction stays for 1min, and the injection is continued for 10min. The reaction solution is analyzed by GC, and the raw material conversion rate is 99%. The reaction solution is filtered, and the filtrate is analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate is 92%.

[0083] Embodiment 20

[0084] Dissolve 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.01mmol) manganese sulfate, 0.003g (0.024mmol) pyridine-2-carboxylic acid in 20ml ethanol and stir; dissolve sodium phosphate-sodium dihydrogen phosphate buffer solution (pH=6.2) in 6ml 30% hydrogen peroxide solution, use double pump injection, injection flow rate ratio: 3.3:1, reaction residence time 1.5min, continuous injection 10min. The reaction solution was analyzed by GC, and the raw material conversion rate was 99%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 87%.

[0085] Embodiment 21

[0086] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.01mmol) manganese sulfate, 0.003g (0.024mmol) pyridine-2-carboxylic acid, dissolved in a mixed solvent of 10ml methanol and 10ml acetone, stirred; sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2) was dissolved in 6ml 30% hydrogen peroxide solution, and a double pump was used for injection, the injection flow rate ratio was: 3.3:1, the reaction residence time was 30s, and the injection was continued for 10min. The reaction solution was analyzed by GC, and the raw material conversion rate was 99%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 89%.

[0087] Embodiment 22

[0088] 32.4g (90.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.06g (0.02mmol) sodium phosphotungstate, 0.006g (0.048mmol) pyridine-2-carboxylic acid, dissolved in 100ml methanol, stirred; sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2) dissolved in 60ml 30% hydrogen peroxide solution, using double pump injection, injection flow rate ratio: 3:1, reaction residence time 5min, continuous injection 30min, the reaction solution was analyzed by GC, the raw material conversion rate was 99%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 89%.

[0089] Embodiment 23

[0090] 100.0g (400.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.3g (0.1mmol) sodium phosphotungstate, 0.3g (0.24mmol) pyridine-2-carboxylic acid, sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2) were dissolved in 20mL DMF (N,N-dimethylformamide), stirred, the system temperature was 10°C, and then 200ml of 30% hydrogen peroxide solution was slowly added to the DMF solution, and the addition was completed in 4 hours, and the reaction was continued for 2 hours. The reaction solution was analyzed by GC, and the raw material conversion rate was 99%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 91%.

[0091] Embodiment 24

[0092] 600.0g (2.40mol) 1,3,5-tri-(propylene)-isocyanurate, 0.6g (0.2mmol) sodium phosphotungstate, 0.6g (0.48mmol) pyridine-2-carboxylic acid, dissolved in 4L methanol, stirred; sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2) was dissolved in 1000ml 35% hydrogen peroxide solution, using double pump injection, injection flow rate ratio: 3:1, reaction residence time 1min, continuous injection 80min. The reaction solution was analyzed by GC, and the raw material conversion rate was 99%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 95%.

[0093] Embodiment 25

[0094] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.01mmol) sodium phosphotungstate, 0.003g (0.05mmol) ethanolamine, sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2), dissolved in 20mL ethyl acetate, stirred, the system temperature was 20°C, and then 6ml 30% hydrogen peroxide solution was slowly added to the ethyl acetate solution, and the addition was completed in 3 hours, and the reaction was continued for another 3 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 91%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 78%.

[0095] Embodiment 26

[0096] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.01mmol) sodium phosphotungstate, 0.003g (0.05mmol) ethanolamine, sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2), dissolved in 20mL chloroform, stirred, the system temperature was 20°C, and then 6ml 30% hydrogen peroxide solution was slowly added to the chloroform solution, and the addition was completed in 3 hours, and the reaction was continued for another 3 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 82%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 67%.

[0097] Embodiment 27

[0098] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.01mmol) sodium phosphotungstate, 0.003g (0.05mmol) imidazole, 0.038g (0.2mmol) sodium sulfate, dissolved in 20mL dioxane, stirred, the system temperature was 20°C, and then 6ml 30% hydrogen peroxide solution was slowly added to the solution, and the addition was completed in 3 hours, and the reaction was continued for another 3 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 99%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 92%.

[0099] Embodiment 28

[0100] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.01mmol) sodium phosphotungstate, 0.003g (0.05mmol) methylimidazole, 0.136g (0.2mmol) sodium formate were dissolved in 20mL ethanol / chloroform, stirred, the system temperature was 20°C, and then 6ml 30% hydrogen peroxide solution was slowly added to the solution, and the addition was completed in 3 hours, and the reaction was continued for another 3 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 99%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 84%.

[0101] Embodiment 29

[0102] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.01mmol) sodium phosphotungstate, 0.003g (0.05mmol) imidazole, 0.038g (0.2mmol) sodium sulfate, dissolved in 20mL dioxane, stirred, the system temperature was 20°C, and then 6ml 30% hydrogen peroxide solution was slowly added to the solution, and the addition was completed in 3 hours, and the reaction was continued for another 3 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 99%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 92%.

[0103] Embodiment 30

[0104] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.031g (0.01mmol) 2-chloronicotinic acid, 0.003g (0.05mmol) N,N-dimethylbenzylamine, 0.038g (0.2mmol) sodium bisulfate were dissolved in 20mL ethanol / acetone solution, stirred, the system temperature was 20°C, and then 6ml 30% hydrogen peroxide solution was slowly added to the solution, and the addition was completed in 3 hours, and the reaction was continued for 2 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 99%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 91%.

[0105] Embodiment 31

[0106] 2.24g (9.0mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.03g (0.01mmol) sodium phosphotungstate, 0.003g (0.05mmol) imidazole, 0.038g (0.2mmol) sodium sulfate, 0.038g (0.2mmol) sodium benzoate, dissolved in 20mL methanol / acetone solution, stirred, system temperature 30°C, then slowly added 6ml 30% hydrogen peroxide solution to the solution, dripped over 1.5 hours, and continued to react for 1 hour. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 99%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 89%.

[0107] Embodiment 32

[0108] 22.4g (90mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.3g (0.1mmol) sodium phosphotungstate, 0.03g (0.5mmol) 2-chloronicotinic acid, 0.12g (2mmol) sodium acetate were dissolved in 200mL toluene / ethanol, stirred, the system temperature was 90°C, and then 60ml of 30% hydrogen peroxide solution was slowly added to the solution, and the addition was completed in 3 hours, and the reaction was continued for another 3 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 99%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 73%.

[0109] Embodiment 33

[0110] 22.4g (90mmol) 1,3,5-tri-(propylene)-isocyanurate, 0.6g (0.1mmol) cerium nitrate, lanthanum nitrate (1:1), 0.03g (0.5mmol) imidazole, 0.12g (2mmol) sodium acetate, dissolved in 200mL methanol / acetone, stirred, the system temperature was 60℃, and then 60ml 30% hydrogen peroxide solution was slowly added to the solution, and the addition was completed in 3 hours, and the reaction was continued for 4 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 98%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 86%.

[0111] Embodiment 34

[0112] 26.2g (90mmol) 1,3,5-tri-(butenyl)-isocyanurate, 0.6g (0.1mmol) cerium nitrate, lanthanum nitrate (1:1), 0.03g (0.5mmol) imidazole, 0.12g (2mmol) sodium acetate, dissolved in 200mL methanol / acetone, stirred, the system temperature was 60℃, and then 60ml 30% hydrogen peroxide solution was slowly added to the solution, and the addition was completed in 3 hours, and the reaction was continued for 4 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 98%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(3,4-epoxypropyl)-isocyanurate was 88%.

[0113] Embodiment 34

[0114] 26.2g (90mmol) 1,3,5-tri-(butenyl)-isocyanurate, 0.6g (0.1mmol) cerium nitrate, lanthanum nitrate (1:1), 0.03g (0.5mmol) imidazole, 0.12g (2mmol) sodium acetate, dissolved in 200mL methanol / acetone, stirred, the system temperature was 60℃, and then 60ml 30% hydrogen peroxide solution was slowly added to the solution, and the addition was completed in 3 hours, and the reaction was continued for 4 hours. After the reaction was completed, the reaction solution was analyzed by GC, and the raw material conversion rate was 98%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(3,4-epoxypropyl)-isocyanurate was 88%.

[0115] Embodiment 35

[0116] 600.0g (2.40mol) 1,3,5-tri-(propylene)-isocyanurate, 0.6g (0.2mmol) sodium phosphotungstate, 0.6g (0.48mmol) pyridine-2-carboxylic acid, dissolved in 4 liters of ethanol / toluene solvent, stirred; sodium phosphate-sodium dihydrogen phosphate buffer solution (pH = 6.2) was dissolved in 1000 ml of 35% hydrogen peroxide solution, using a double pump injection, the injection flow rate ratio is: 3:1, the reaction residence time is 30s, and the injection is continued for 20min. The reaction solution was analyzed by GC, and the raw material conversion rate was 99%. The reaction solution was filtered, and the filtrate was analyzed by HPLC, confirming that the HPLC yield of 1,3,5-tri-(2,3-epoxypropyl)-isocyanurate was 93%.

[0117] The above describes the specific embodiments of the present invention. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art can make various modifications or variations within the scope of the claims, which does not affect the essence of the present invention. The above preferred features can be used in any combination without conflicting with each other.

Claims

1. A method for preparing an epoxy compound, characterized in that: include: The triolefin isotrimer acid ester compound I undergoes an oxidation reaction with hydrogen peroxide under the action of a catalyst, an auxiliary catalyst and a salt to obtain a triglycidyl isocyanate compound II; The structural formulas of triolefin isotrimer ester compound I and triglycidyl isocyanate compound II are as follows: Among them, R in I is methyl, n1 、 n2 、 n3 is any integer from 1 to 3; R in II is methyl, n1 、 n2 、 n3 is any integer from 1 to 3; Adopt microchannel continuous flow reaction; The catalyst is pyridine-2-carboxylic acid; The auxiliary catalyst is sodium phosphotungstate or manganese sulfate; The salt is sodium phosphate-sodium dihydrogen phosphate; The solvent used is any one of acetonitrile, ethanol, methanol / acetone mixed solvent, methanol, and ethanol / toluene mixed solvent.

2. The method for preparing an epoxy compound according to claim 1, characterized in that: The molar ratio of the triene isotrimer acid ester compound I to hydrogen peroxide is 1:(3-5), and the concentration of hydrogen peroxide is 5%-50%.

3. The method for preparing an epoxy compound according to claim 1, characterized in that: The molar ratio of the triene isotrimer acid ester compound I to the catalyst is 1:(0.001-0.5).

4. The method for preparing an epoxy compound according to claim 1, characterized in that: The molar ratio of the triolefin isotrimer acid ester compound I to the auxiliary catalyst is 1:(0.001-0.5).

5. The method for preparing an epoxy compound according to claim 1, characterized in that: The molar ratio of the triene isotrimer acid ester compound I to the salt is 1:(0.001-1).

6. The method for preparing an epoxy compound according to claim 1, characterized in that: The reaction temperature of the oxidation reaction is -10 to 100°C; the reaction time is 30s to 10h.

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