Synthesis method of isocyanide urate substance

Abstract

The invention discloses a synthesis method of an isocyanide urate substance, which is characterized in that 2, 4, 6-triallyloxy-1, 3, 5-triazine is subjected to a rearrangement reaction in a toluene solvent under the common catalytic action of copper-loaded zeolite and ultraviolet rays to prepare the isocyanide urate substance containing a triazine structure, and the copper-loaded zeolite, the 2, 4, 6-triallyloxy-1, 3, 5-triazine, the copper-loaded zeolite and the 2, 4, 6-triallyloxy-1, 3, 5-triazine are subjected to a rearrangement reaction in a toluene solvent to prepare the isocyanide urate substance containing the triazine structure. When the mass ratio of 1, 3, 5-triazine to toluene is 1: (1.2-1.4): (1.4-1.6), the obtained product is diallyl isocyanurate; when the mass ratio is 1: (0.6-0.8): (1.2-1.4), the obtained product is allyl isocyanurate; according to the method, the pertinence of the rearrangement reaction is improved, no water is used in the reaction process, the stability of the raw materials is improved, the generation of byproducts is effectively reduced, and the high-purity monoallyl isocyanurate or diallyl isocyanurate product can be prepared; according to the method, too high temperature and high pressure are not used, the safety is higher, the reaction time is short, the production efficiency is improved, and the method is more suitable for industrial popularization and application.

Description

Technical Field

[0001] This invention belongs to the field of electronic chemistry and relates to a method for preparing a precursor of a photosensitive resin coating raw material, and more particularly to a method for synthesizing isocyanate urate substances. Background Technology

[0002] High molecular weight monomers of a series of triazine-containing aromatic heterocyclic multifunctional olefins, such as allyl isocyanurate, diallyl isocyanurate, and triallyl isocyanurate, are a class of widely used fine chemical products. Triallyl isocyanurate, in particular, can be used in combination with organic peroxides such as DCP for crosslinking thermoplastic materials such as polyolefins, polyvinyl chloride, polyesters, polyamides, ethylene propylene rubber, and silicone rubber. The triazine structure in these substances also improves the heat resistance, mechanical strength, oil resistance, and gas permeability of crosslinked products. They can also polymerize with other unsaturated monomers to form transparent, hard, and wear-resistant polymers, serving as carriers for liquid and gas chromatography columns. The product of bromine addition is a novel polymer flame retardant. In the field of electronic chemistry, allyl isocyanurate and diallyl isocyanurate offer improved heat resistance and thermal expansion properties, and are therefore used in the manufacture of high-performance electronic components. In addition to the chemical bonds between alkoxy groups and curing agents, these products exhibit enhanced heat resistance and thermal expansion properties. They also possess excellent strength and, when applied to metal films, can demonstrate excellent adhesion to the metal film through chemical bonding with the metal film surface and alkoxy groups.

[0003] Currently, most products produced and sold in the market are triallyl isocyanurates, and research on the preparation process of these products also focuses on triallyl isocyanurates. For example, Chinese invention patent application No. 201210344398.1, entitled "A Method for Preparing Triallyl Isocyanurate," discloses adding sodium isocyanate and a catalyst to a solvent, reacting by dropwise adding allyl chloride at a temperature of 70℃~105℃, reacting for 4h~8h, cooling to room temperature, filtering to remove the solid phase, and distilling the filtrate after solvent recovery to obtain the product. The catalyst used in this document is a reducing catalyst, specifically copper or cuprous chloride, and the transfer catalyst is triethylamine, tributylamine, or pyridine; the solvent is a polar aprotic solvent such as N,N-dimethylformamide, dimethyl sulfoxide, N-methylacetamide, or acetonitrile. However, the purity of the product obtained by this process can only reach 98%, because the unavoidable disubstituted and monosubstituted byproducts generated in the process increase the difficulty of purification. However, it is quite difficult to prepare disubstituted or monosubstituted products by controlling the proportion of raw materials based on the above synthetic route, because allyl chloride is easily hydrolyzed in strong alkaline aqueous solution to generate allyl alcohol, and the raw materials are unstable.

[0004] Another type of reaction route uses triallyl cyanurate as a raw material, in Cu 2+Diallyl isocyanurates are prepared by rearrangement under catalytic action and high temperature conditions. For example, Likhterov et al. (Likhterov VR, Klenovich SV, Etlis VS, et al. Inter-and intramolecular rearrangement of triallyl cyanurates[J]. Khimiya Geterotsiklicheskikh Soedinenii, 1988(3), 376-9.) added triallyl cyanurate (i.e., 2,4,6-triallyloxy-1,3,5-triazine) and copper chloride into the reactor at one time. During heating, byproducts such as allyl isocyanurate are generated. However, when this method is applied to industrial production, the heat of reaction in the reactor is difficult to remove, which poses a risk of runaway reaction and may easily lead to safety accidents such as material spillage. In fact, according to the principle of rearrangement reaction, a major problem in preparing such products is that it is difficult to control the accuracy of substitution, which easily leads to other substitution byproducts. Moreover, the byproducts have a high degree of structural similarity to the main product, making them difficult to purify later. In addition, high temperatures can easily trigger polymerization reactions and produce polymerization byproducts, making it difficult to prepare high-purity products of this type. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art. This invention provides a method for synthesizing isocyanate urate substances with high reaction selectivity, high product purity, and suitability for industrial production.

[0006] The present invention provides a method for synthesizing isocyanate urates. The key aspect is that the above-mentioned synthesis method involves a rearrangement reaction of 2,4,6-trienylpropoxy-1,3,5-triazine in toluene solvent under the combined catalysis of copper-supported zeolite and ultraviolet light, to prepare isocyanate urates containing a triazine structure. When the mass ratio of copper-supported zeolite, 2,4,6-trienylpropoxy-1,3,5-triazine, and toluene is 1:1.2–1.4:1.4–1.6, the product obtained is diallyl isocyanurate; when the mass ratio is 1:0.6–0.8:1.2–1.4, the product obtained is monoallyl isocyanurate.

[0007] Specifically, the preparation method of the above-mentioned copper-loaded zeolite is as follows:

[0008] Crush the zeolite into powder with a particle size of 100-120 mesh, add it to a saturated sodium chloride solution at a solid-liquid ratio of 1g / 10mL, boil it, pour off the turbid liquid, wash it with distilled water, repeat the operation once or twice, and then put the zeolite in an oven to dry it for later use.

[0009] Take 1 part by weight of the above-treated zeolite, soak it in 3 parts by weight of copper chloride aqueous solution, heat to 40℃~60℃, adjust the pH to slightly acidic, soak for 8h~12h, centrifuge, and wash with distilled water until no Cu is found in the washing solution. 2+ .

[0010] Preferably, the concentration of the above-mentioned copper chloride aqueous solution is 6 g / L to 7 g / L.

[0011] Preferably, the pH value of the above-mentioned pH ranges from slightly acidic to 5.5 to 6.5.

[0012] Furthermore, the specific preparation process of the above-mentioned synthesis method is as follows:

[0013] The reaction column was packed with copper-loaded zeolite and flushed with anhydrous ethanol. 2,4,6-trienylpropoxy-1,3,5-triazine was then dissolved in toluene and passed through the reaction column. After the reaction started, the reaction column was irradiated with ultraviolet light for a certain period of time and then heated to reflux. After the reaction was completed, the reaction solution was filtered, and the filtrate was washed with dichloromethane and water and then dried to obtain the target product.

[0014] Preferably, the reaction temperature is 110°C and the reaction time is 2h to 4h.

[0015] Optimal, the intensity of the aforementioned ultraviolet radiation is 70 μW / cm. 2 ~80μW / cm 2 The reaction column was irradiated with ultraviolet light for 0.5 to 1 hour after the start of the reaction.

[0016] Compared with the prior art, the present invention has the following advantages:

[0017] This invention utilizes specially prepared copper-supported zeolite and ultraviolet light of a certain intensity for co-catalysis, enabling a rearrangement reaction of 2,4,6-triallyloxy-1,3,5-triazine in toluene solvent. The use of ultraviolet-assisted catalysis in this invention improves the selectivity of the rearrangement reaction. Furthermore, by precisely controlling the ratio of copper-supported zeolite to starting materials, this invention further enhances the specificity of the rearrangement reaction, facilitating the production of the target product. The absence of water in the reaction process improves the stability of the raw materials and effectively reduces the generation of byproducts. Therefore, subsequent purification processes do not require recrystallization; only simple purification methods such as washing and drying are needed to prepare high-purity monoallyl isocyanurate or diallyl isocyanurate products.

[0018] The preparation process of the copper-loaded zeolite in this invention does not use Cu. 2+ Instead of direct displacement of the solution, the process involves first obtaining a sodium-loaded zeolite intermediate, which significantly improves the efficiency of Cu. 2+The loading rate is high, and the microporous environment of the zeolite increases the contact area and contact time between the catalyst and the substrate, thereby improving catalytic efficiency and reducing the total amount of copper chloride used. The copper-loaded zeolite prepared by this invention has stable quality, which is more conducive to controlling the material ratio and improving the controllability of production operations. The used zeolite can be recycled and reused, further realizing recycling.

[0019] The present invention does not use excessively high temperatures and pressures during the reaction process, resulting in higher safety, shorter reaction time, improved production efficiency, and greater suitability for industrial application. Attached Figure Description

[0020] Figure 1 This is the NMR spectrum of an allyl isocyanurate sample of the present invention.

[0021] Figure 2 This is the NMR spectrum of the diallyl isocyanurate sample of this invention.

[0022] Figure 3 This is the gas chromatography-mass spectra of an allyl isocyanurate sample of the present invention.

[0023] Figure 4 This is the gas chromatography-mass spectra of the diallyl isocyanurate sample of this invention.

[0024] Figure 5 This is a high-performance gas chromatography (HPLC) spectrum of an allyl isocyanurate sample of the present invention.

[0025] Figure 6 This is a high-performance gas chromatography (HPLC) spectrum of the diallyl isocyanurate sample of the present invention. Detailed Implementation

[0026] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0027] Unless otherwise specified in the examples, the procedures can be followed according to conventional conditions; unless the manufacturers of the reagents or instruments used are specified, they are all conventional products that can be purchased commercially.

[0028] For ease of description, the following is in parts by weight.

[0029] Example 1

[0030] S1. Crush the artificial zeolite into powder with a particle size of 100-120 mesh, add it to a saturated sodium chloride solution at a solid-liquid ratio of 1g / 10mL, boil it on an electric furnace and maintain it for 45min, pour off the turbid liquid, wash it with distilled water, repeat the operation twice, and finally put the zeolite in an oven to dry at 45℃ for later use.

[0031] S2. Take one part of the zeolite treated above and soak it in three parts of copper chloride aqueous solution with a concentration of 6.5 g / L. Heat to 50°C, pH 6, soak for 10 h, centrifuge, and wash with distilled water until no Cu is found in the washing solution. 2+ Copper-loaded zeolite was prepared.

[0032] S3. Pack the reaction column with the copper-loaded zeolite treated as described above, flush the column with anhydrous ethanol, then dissolve 0.7 parts of 2,4,6-trienylpropoxy-1,3,5-triazine in 1.2 parts of toluene and pass the solution into the reaction column. Heat the reaction column to approximately 110°C and reflux for 3 hours. After the reaction begins, irradiate the reaction column with ultraviolet light for 45 minutes at an intensity of 75 μW / cm. 2 ;

[0033] S4. After the reaction is complete, the reaction solution is filtered, and the filtered material is washed with dichloromethane and water and then dried to obtain the target product, allyl isocyanurate sample 1.

[0034] Example 2

[0035] S1. Crush the artificial zeolite into powder with a particle size of 100-120 mesh, add it to a saturated sodium chloride solution at a solid-liquid ratio of 1g / 10mL, boil it on an electric furnace and maintain it for 0.5h, pour off the turbid liquid, wash it with distilled water, repeat the operation twice, and finally put the zeolite into an oven to dry at 50℃ for later use.

[0036] S2. Take one part of the zeolite treated above and soak it in three parts of copper chloride aqueous solution with a concentration of 6 g / L. Heat the solution to 60°C and pH 6.5, soak for 12 hours, centrifuge, and wash with distilled water until no Cu is found in the washings. 2+ Copper-loaded zeolite was prepared.

[0037] S3. Pack the reaction column with the copper-loaded zeolite treated as described above, flush the column with anhydrous ethanol, then dissolve 0.8 parts of 2,4,6-trienylpropoxy-1,3,5-triazine in 1.3 parts of toluene and pass the solution into the reaction column. Heat the reaction column to approximately 110°C and reflux for 4 hours. After the reaction begins, irradiate the reaction column with ultraviolet light for 1 hour at an intensity of 70 μW / cm. 2 ;

[0038] S4. After the reaction is complete, the reaction solution is filtered, and the filtered material is washed with dichloromethane and water and then dried to obtain the target product, allyl isocyanurate sample 2.

[0039] Example 3

[0040] S1. Crush the artificial zeolite into powder with a particle size of 100-120 mesh, add it to a saturated sodium chloride solution at a solid-liquid ratio of 1g / 10mL, boil it on an electric furnace and maintain it for 1 hour, pour off the turbid liquid, wash it with distilled water, repeat the operation once, and finally put the zeolite in an oven to dry at 40℃ for later use.

[0041] S2. Take one part of the zeolite treated above and soak it in three parts of copper chloride aqueous solution with a concentration of 7 g / L. Heat to 40°C, pH 5.5, soak for 8 hours, centrifuge, and wash with distilled water until no Cu is found in the washing solution. 2+ Copper-loaded zeolite was prepared.

[0042] S3. Pack the reaction column with the copper-loaded zeolite treated as described above, flush the column with anhydrous ethanol, then dissolve 0.6 parts of 2,4,6-trienylpropoxy-1,3,5-triazine in 1.4 parts of toluene and pass the solution into the reaction column. Heat the reaction column to approximately 110°C and reflux for 2 hours. After the reaction begins, irradiate the reaction column with ultraviolet light for 0.5 hours at an intensity of 80 μW / cm. 2 ;

[0043] S4. After the reaction is complete, the reaction solution is filtered, and the filtered material is washed with dichloromethane and water and then dried to obtain the target product, allyl isocyanurate sample 3.

[0044] Example 4

[0045] The specific preparation process is the same as in Example 1, except that in "S3, Step", 1.3 parts of 2,4,6-triallyloxy-1,3,5-triazine are dissolved in 1.5 parts of toluene and passed into a reaction column. The subsequent preparation process is the same as in Example 1. The target product is diallyl isocyanurate sample 1.

[0046] Example 4

[0047] The specific preparation process is the same as in Example 2, except that in "S3, Step", 1.2 parts of 2,4,6-triallyloxy-1,3,5-triazine are dissolved in 1.6 parts of toluene and passed into a reaction column. The subsequent preparation process is the same as in Example 2. The target product is diallyl isocyanurate sample 2.

[0048] Example 5

[0049] The specific preparation process is the same as in Example 3, except that in "S3, Step", 1.4 parts of 2,4,6-triallyloxy-1,3,5-triazine are dissolved in 1.4 parts of toluene and passed into the reaction column. The subsequent preparation process is the same as in Example 3. The target product is diallyl isocyanurate sample 3.

[0050] Comparative Example 1

[0051] The specific preparation process is the same as in Example 1, except that in "S3, Step", the reaction column is not irradiated with ultraviolet light, and the target product - allyl isocyanurate reference standard 1 is prepared.

[0052] The specific preparation process is the same as in Example 4, except that in "S3, Step", the reaction column is not irradiated with ultraviolet light, and the target product diallyl isocyanurate reference standard 1 is prepared.

[0053] Comparative Example 2

[0054] The specific preparation process is the same as in Example 1, except that in "S3, Step", 1.0 part of 2,4,6-trienylpropoxy-1,3,5-triazine is dissolved in 1.5 parts of toluene and passed into a reaction column to prepare the target product, allyl isocyanurate reference standard 2.

[0055] Comparative Example 3

[0056] The specific preparation process is the same as in Example 4, except that in "S3, Step", the reaction column is not rinsed with anhydrous ethanol to prepare the target product diallyl isocyanurate reference standard 2.

[0057] Analysis and Testing

[0058] The samples prepared in this invention were analyzed by 1H NMR and HPLC-MS / MS, confirming that the structures of the samples obtained in Examples 1 to 3 conform to the characteristics of allyl isocyanurate, and the structures of the samples obtained in Examples 4 to 6 conform to the characteristics of diallyl isocyanurate. Some of the test spectra are shown in the appendix. Figures 1-4 .

[0059] The purity of the samples was determined by high-performance gas chromatography (HPLC), and the yield was calculated using the following formula. The results are shown in Table 1, and some test chromatograms are shown in the appendix. Figure 5 and 6 .

[0060] The yield calculation formula is:

[0061] Product yield = Actual weight of the obtained sample (g) / Theoretical yield (g) calculated based on the amount of 2,4,6-trienylpropoxy-1,3,5-triazine used × 100%.

[0062] Table 1: Summary of Purity and Yield Results

[0063] Sample number Product purity (%) Yield (%) Allyl isocyanurate sample 1 99.60 84.9 Allyl isocyanurate sample 2 99.53 83.1 Allyl isocyanurate sample 3 99.56 83.6 Diallyl isocyanurate sample 1 99.63 85.1 Diallyl isocyanurate sample 2 99.55 82.3 Diallyl isocyanurate sample 3 99.58 83.8 Allyl isocyanurate reference standard 1 86.21 61.2 Allyl isocyanurate reference standard 2 63.45 43.7 Diallyl isocyanurate reference standard 1 85.32 60.5 Diallyl isocyanurate reference standard 2 90.17 69.3

[0064] As shown in Table 1, this invention uses 2,4,6-trienylpropoxy-1,3,5-triazine as the starting material, and initiates a rearrangement reaction under the co-catalysis of copper-supported zeolite and ultraviolet light. The rearrangement is achieved by controlling the Cu content. 2+ The amount of [specific ingredient] used can yield either allyl isocyanurate or diallyl isocyanurate, two rearrangement products respectively. The purity of the product obtained by this invention can be consistently above 99.5%, with a maximum of 99.6%, and the highest product yield can reach about 85%. By changing the catalytic mode of the rearrangement reaction, using only Cu [specific ingredient]... 2+ Initiating the reaction can affect the purity and yield of the product. The study also found that if only Cu is used... 2+ Initiate the reaction by increasing Cu 2+ Using more raw materials to increase product purity will increase raw material costs and hinder industrialization.

[0065] In this invention, rinsing the reaction column with anhydrous ethanol serves two purposes: firstly, it activates the reaction column; secondly, it removes water from the zeolite micropores, reducing the occurrence of side reactions related to raw material decomposition. The ethanol remaining in the silver-loaded zeolite enhances the Cu content on the zeolite. 2+ The high solubility in solvents enhances the catalytic effect. Furthermore, this invention has strict requirements on the proportions of the materials; only by controlling the amounts of copper-supported zeolite and 4,6-trienylpropoxy-1,3,5-triazine within a suitable range can the target product with the required purity be prepared.

[0066] Impurity analysis was performed on allyl isocyanurate sample 1 and diallyl isocyanurate sample 1, and the results are shown in Tables 2 and 3, respectively.

[0067] Table 2: Impurity Analysis Table for Allyl Isocyanurate Samples

[0068]

[0069] Table 3: Impurity Analysis Table for Diallyl Isocyanurate Samples

[0070]

[0071] In Table 2, peak 1 is the target product (monallyl isocyanurate), peak 2 is diallyl isocyanurate, and peak 3 is triallyl isocyanurate. In Table 3, peak 1 is the target product (dialyl isocyanurate), peak 2 is triallyl isocyanurate, and peak 3 is the starting material 2,4,6-triallylpropoxy-1,3,5-triazine. Based on the impurity analysis in Tables 2 and 3, it can be seen that the byproducts of this reaction consist only of a small amount of rearrangement products that are not the target product and residual starting materials. There are no other byproducts, such as products from the decomposition of the starting materials. The product has high purity, few types of impurities, and low impurity content.

Claims

1. A method for synthesizing isocyanurate species, characterized by, The synthetic method 2,4,6-triallyloxy-1,3,5-triazine is rearranged in toluene solvent under the catalysis of copper-loaded zeolite and ultraviolet light, and an isocyan uric acid ester containing triazine structure is prepared, when the mass ratio of copper-loaded zeolite, 2,4,6-triallyloxy-1,3,5-triazine and toluene is 1:1.2-1.4:1.4-1.6, the product is diallyl isocyanurate, and when the mass ratio is 1:0.6-0.8:1.2-1.4, the product is monallyl isocyanurate.

2. The method for synthesizing isocyanate urate substances according to claim 1, characterized in that, The preparation method of the copper-loaded zeolite is as follows: The zeolite is crushed into a powder with a particle size of 100-120 meshes, and is put into a saturated sodium chloride solution at a solid-liquid ratio of 1g / 10mL, boiled, and the turbid liquid is poured off, and the zeolite is washed with distilled water, and after repeating the operation 1-2 times, the zeolite is dried in an oven and is ready for use; The treated zeolite of 1 mass part is immersed in a copper chloride aqueous solution of 3 mass parts, heated to 40-60°C, adjusted to a slightly acidic pH, and immersed for 8-12 hours. The solution is centrifuged and washed with distilled water until the wash water is free of Cu 2+ .

3. The method of claim 2, wherein the isocyanurate compound is synthesized by the reaction of the compound of formula (I) with the compound of formula (II) in the presence of a base. The concentration of the copper chloride aqueous solution is 6-7g / L.

4. The method of claim 2, wherein the isocyanurate compound is synthesized by the reaction of the compound of formula (2) with the compound of formula (3) in the presence of a base. The pH is slightly acidic, and the pH value is 5.5-6.

5.

5. The method for synthesizing isocyanate urate substances according to claim 1, characterized in that, The specific preparation process of the synthetic method is as follows: The copper-loaded zeolite is filled in a reaction column, and anhydrous ethanol is used to flush the column, then 2,4,6-triallyloxy-1,3,5-triazine is dissolved in toluene and is passed through the reaction column, after the reaction starts, the reaction column is irradiated with ultraviolet light for a certain time, and the reaction column is heated for reflux reaction, after the reaction is completed, the reaction liquid is filtered, and the filtrate is washed with dichloromethane and water, and is dried to obtain the target product.

6. The method of claim 5, wherein the isocyanurate compound is synthesized by the reaction of the compound of formula (I) with the compound of formula (II) in the presence of a base. The temperature of the reaction is 110°C, and the reaction time is 2-4h.

7. The method of claim 5, wherein the isocyanurate compound is synthesized by the reaction of the compound of formula (I) with the compound of formula (II) in the presence of a base. The intensity of the ultraviolet rays is 70 μW / cm 2 ~ 80 μW / cm 2 The time of irradiation of the reaction column with ultraviolet rays is 0.5 to 1 hour after the start of the reaction.

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