Preparation method of propargyl glycidyl ether
By using activated clay as a catalyst in the preparation of propargyl glycidyl ether, the problems of catalyst recovery and low efficiency are solved, the preparation and environmental protection of high-purity products are achieved, and it is suitable for industrial production.
Patent Information
- Application Number
- CN202411352620.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-26
- Publication Date
- 2025-01-17
AI Technical Summary
In the prior art, the phase transfer catalyst of propargyl glycidyl ether cannot be recovered, the catalytic efficiency is low, resulting in low reaction yield and serious environmental pollution.
Using activated clay as a catalyst, propyne alcohol and epoxychlorohydrin were reacted with alkaline solution at 25 to 75°C, the catalyst was recovered by dropwise addition and filtration, and reused, and distilled to obtain high-purity propargyl glycidyl ether.
It improves product yield and quality, reduces wastewater and waste slag emissions brought by catalysts, reduces environmental pollution, and is suitable for industrial production.
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Abstract
Description
Technical Field
[0001] The present application relates to the technical field of material synthesis, and in particular to a method for preparing propargyl glycidyl ether. Background Art
[0002] Propargyl glycidyl ether (1-glycidyloxy-2-propyne), molecular formula: C6H8O2, molecular weight: 112.12, CAS number: 18180-30-8, is a colorless transparent liquid. Propargyl glycidyl ether is mainly used in the electroplating industry, and acts as a brightener in the nickel plating process; because propargyl glycidyl ether contains acetylenic bonds and epoxy groups, it can also be used as a reactive diluent in electronic packaging, coatings and other industries.
[0003] At present, the synthesis of glycidyl ether is mainly divided into one-step method and two-step method. The one-step method is to use phase transfer catalyst to directly catalyze the reaction of raw alcohol and epichlorohydrin to obtain glycidyl ether. The advantages are shortening the reaction time and reducing the reaction steps; but the disadvantage is that the reaction yield is generally not high. For example, Lei Tao published "Synthesis of Ethylene Glycol Methyl Ether Glycidyl Ether by Phase Transfer Catalysis" in 2007, which mentioned that the yield of ethylene glycol methyl ether glycidyl ether synthesized by phase transfer catalysis was 71.0%. The two-step method is that the first step uses Lewis acid as a catalyst to make the raw alcohol and epichlorohydrin generate intermediate products, and then close the loop to produce glycidyl ether under alkaline conditions. The advantage is that the yield of the obtained glycidyl ether is high, but the disadvantage is that Lewis acid corrodes the equipment, causing serious pollution and a long reaction time.
[0004] It can be seen that the prior art, whether using a one-step method or a two-step method, has certain defects, especially the problem that the propargyl glycidyl ether phase transfer catalyst cannot be recovered. Therefore, it is necessary to propose a new method for preparing propargyl glycidyl ether to solve the shortcomings of the prior art. Summary of the invention
[0005] In view of the technical problems existing in the background technology, the present application provides a method for preparing propargyl glycidyl ether, aiming to solve the technical problems in the prior art that the propargyl glycidyl ether phase transfer catalyst cannot be recovered and has low catalytic efficiency.
[0006] The present application provides a method for preparing high-purity propargyl glycidyl ether, comprising the following steps: at 25-75° C., propargyl alcohol, epichlorohydrin and a catalyst are mixed and an alkali solution is added dropwise for reaction to obtain a mixed solution; the mixed solution is dissolved in water and filtered, the catalyst in the precipitate is recovered, and the liquid is layered to obtain a crude product of propargyl glycidyl ether; the crude product of propargyl glycidyl ether is distilled to obtain high-purity propargyl glycidyl ether. In the present application, the catalyst is preferably activated clay, which has strong catalytic activity, reduces the reaction temperature, improves the yield and quality of the product, is conducive to scale-up production, and reduces the discharge of wastewater and waste residues caused by the catalyst.
[0007] Specifically, during the preparation of the mixed solution, the conditions for adding the alkali solution are: the dropping temperature is 35 to 45° C., and the dropping time is 4 to 8 h.
[0008] Specifically, during the preparation of the mixed solution, after the alkali solution is added, the reaction is continued at 35 to 45° C. for 1.0 to 2.0 h.
[0009] Preferably, the molar ratio of propargyl alcohol to epichlorohydrin is 1:1 to 1:10.
[0010] Preferably, the mass ratio of activated clay to propargyl alcohol is (0.01-0.1):1.
[0011] Specifically, water is added to the mixed solution to dissolve it and the solution is filtered while hot, and the activated clay in the precipitate is recovered and reused for the preparation of subsequent mixed solutions.
[0012] Preferably, the activated clay is reused 1 to 20 times.
[0013] Preferably, the alkali solution is any one of sodium hydroxide solution or potassium hydroxide solution or a mixture of the two.
[0014] Preferably, the distillation conditions are: distillation temperature is 80-90°C, and vacuum degree is -0.095-0.098MPa.
[0015] Compared with the prior art, the beneficial effects of this application include: The present application uses propargyl alcohol and epichlorohydrin as starting raw materials, uses activated clay as a catalyst to obtain a crude product of propargyl glycidol, filters and recovers the catalyst, reuses it, and obtains high-purity propargyl glycidyl ether after distillation; the process of the present application can greatly improve the yield and quality of the product, is conducive to scale-up production, and greatly reduces the discharge of wastewater and waste residues caused by the reaction catalyst, reduces pollution to the environment, and is conducive to the industrial production of high-purity propargyl glycidyl ether.
[0016] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. DETAILED DESCRIPTION
[0017] The following is a detailed description of the embodiments of the technical solution of the present application. The following embodiments are only used to more clearly illustrate the technical solution of the present application, and are therefore only used as examples, and cannot be used to limit the scope of protection of the present application.
[0018] Activated clay is a type of polyoxide composed of various metal oxides (such as SiO2, Al2O3, Fe2O3, MgO, TiO2, CaO, P2O5) coordinated and bridged by oxygen atoms according to a certain structure. In addition, activated clay is insoluble in water, organic solvents and various oils, and swells very little in water and oil. Since the relative density of activated clay is relatively large (2.3~2.5), it is easy to precipitate and separate in organic reaction solutions, easy to post-process and recycle, and does not cause environmental pollution. In this application, the catalyst is preferably activated clay, which has strong catalytic activity, reduces the reaction temperature, improves the yield and quality of the product, is conducive to scale-up production, and reduces the discharge of wastewater and waste residues caused by the catalyst.
[0019] The preparation method of high-purity propargyl glycidyl ether in the present application comprises the following steps: at 25-75°C, propargyl alcohol, epichlorohydrin and a catalyst are mixed and an alkali solution is added dropwise for reaction to obtain a mixed solution; the mixed solution is dissolved in water and filtered, the catalyst in the precipitate is recovered, and the liquid is layered to obtain a crude product of propargyl glycidyl ether; the crude product of propargyl glycidyl ether is distilled to obtain high-purity propargyl glycidyl ether. The specific reaction formula of the preparation method is as follows: .
[0020] The present application uses activated clay as a catalyst to prepare propargyl glycidyl ether, so as to solve the technical problem that the propargyl glycidyl ether phase transfer catalyst cannot be recovered in the prior art, and at the same time reduces the preparation temperature, and improves the yield and effective content.
[0021] Specifically, in terms of mass percentage, the components of activated clay include: SiO2 84%~87%, Al2O3 9%~12%, Fe2O3 0.5%~2%, MgO 0~0.1%, TiO2 0~0.3%, Na2O 0.1%~0.5%, CaO 0.2%~0.7%, P2O 50~0.1% and K2O 0.2%~0.5%.
[0022] Specifically, during the preparation of the mixed solution, the conditions for adding the alkali solution are: the dropping temperature is 35 to 45° C., and the dropping time is 4 to 8 h.
[0023] Specifically, during the preparation of the mixed solution, after the alkali solution is added, the reaction is continued at 35 to 45° C. for 1.0 to 2.0 h.
[0024] Preferably, the molar ratio of propargyl alcohol to epichlorohydrin is 1:1 to 1:10.
[0025] Preferably, the mass ratio of activated clay to propargyl alcohol is (0.01-0.1):1.
[0026] Specifically, water is added to the mixed solution to dissolve it and the solution is filtered while hot, and the activated clay in the precipitate is recovered and reused for the preparation of subsequent mixed solutions.
[0027] Preferably, the activated clay is reused 1 to 20 times.
[0028] Preferably, the alkali solution is any one of sodium hydroxide solution or potassium hydroxide solution or a mixture of the two.
[0029] Preferably, the distillation conditions are: distillation temperature is 80-90°C, and vacuum degree is -0.095-0.098MPa.
[0030] The technical solution of the present application will be described in detail below in conjunction with the embodiments. Specific techniques or conditions not specifically noted in the embodiments are all performed in accordance with the literature in the art or conventional techniques in the art.
[0031] Example 1 Add 92.5g (1.0mol) of epichlorohydrin, 56g (1.0mol) of propargyl alcohol and 2.8g of activated clay into a 500mL four-necked flask, stir evenly, heat to 35°C, slowly drop 137.5g of sodium hydroxide solution (32%), control the dropping temperature at 35-45°C, after the dropwise addition, continue the reaction at 35-45°C for 1 hour, add water to dissolve the salt, filter and recover the catalyst activated clay, separate the liquid, take the organic phase, and perform vacuum distillation to obtain 90.9g of high-purity propargyl glycidyl ether with a yield of 81.2% and a purity of 99.05%.
[0032] Example 2 Add 203.4g (2.2mol) of epichlorohydrin, 112g (2.0mol) of propargyl alcohol and 5.6g of activated clay into a 1L four-necked flask, stir evenly, heat to 35°C, slowly drop 275g of sodium hydroxide solution (32%), control the dropping temperature at 35-45°C, after the dropwise addition, continue the reaction at 35-45°C for 1 hour, add water to dissolve the salt, filter and recover the catalyst activated clay, separate the liquid layers, take the organic phase, and perform vacuum distillation to obtain 208.8g of high-purity propargyl glycidyl ether with a yield of 93.2% and a purity of 99.12%.
[0033] Example 3 Add 370g (4mol) of epichlorohydrin, 112g (2.0mol) of propargyl alcohol and 2.8g of activated clay into a 1L four-necked flask, stir evenly, heat to 35°C, slowly drop 275g of sodium hydroxide solution (32%), control the dropping temperature at 35-45°C, after the dropwise addition, continue the reaction at 35-45°C for 1 hour, add water to dissolve the salt, filter and recover the catalyst activated clay, separate the liquid layers, take the organic phase, and perform vacuum distillation to obtain 209.4g of high-purity propargyl glycidyl ether with a yield of 93.5% and a purity of 99.13%.
[0034] Example 4 Add 203.4g (2.2mol) of epichlorohydrin, 112g (2.0mol) of propargyl alcohol and 5.6g of activated clay into a 1L four-necked flask, stir evenly, heat to 25°C, slowly drop 275g of sodium hydroxide solution (32%), control the dropping temperature at 25-35°C, after the dropwise addition, continue the reaction at 25-35°C for 1 hour, add water to dissolve the salt, filter and recover the catalyst activated clay, separate the liquid layers, take the organic phase, and perform vacuum distillation to obtain 178.1g of high-purity propargyl glycidyl ether with a yield of 79.5% and a purity of 99.07%.
[0035] Example 5 Add 203.4kg (2.2kmol) of epichlorohydrin, 112kg (2.0kmol) of propargyl alcohol and 5.6kg of activated clay into a 1000L four-necked flask, stir evenly, heat to 35°C, slowly drop 275kg of sodium hydroxide solution (32%), control the dropping temperature at 35-45°C, after the dropwise addition, continue the reaction at 35-45°C for 1 hour, add water to dissolve the salt, filter and recover the catalyst activated clay, separate the liquid, take the organic phase, and perform vacuum distillation to obtain 210.8kg of high-purity propargyl glycidyl ether with a yield of 94.1% and a purity of 99.31%.
[0036] Example 5 is equivalent to the scaled-up experiment of Example 2. From the comparison between the two, it can be seen that the present application can further improve the yield in the scaled-up experiment, indicating that the preparation method of the present application does not require precise process control conditions and is suitable for industrial production.
[0037] Example 6 The only difference between this embodiment and embodiment 5 is that the catalyst is activated clay recycled 10 times, and the yield of the obtained product is similar to that of embodiment 5, which also shows that the present application can be applied to scale-up production and the catalyst can be reused.
[0038] Comparative Example 1 The only difference between Comparative Example 1 and Example 2 is that the amount of epichlorohydrin is adjusted to 1.8 mol, that is, propynyl alcohol is in excess, and the other steps and conditions are the same as those in Example 2.
[0039] Comparative Example 2 The difference between Comparative Example 2 and Example 2 is that the activated clay is replaced by tetrabutylammonium bromide as a phase transfer catalyst, and the other steps and conditions are the same as those of Example 2.
[0040] Comparative Example 3 The difference between Comparative Example 3 and Example 2 is that the reaction temperature is adjusted to 55° C., and the other steps and conditions are the same as those in Example 2.
[0041] Comparative Example 4 The difference between Comparative Example 4 and Example 2 is that the amount of alkali solution is adjusted to 225 g, and the other steps and conditions are the same as those in Example 2.
[0042] The results of the above-mentioned Example 2 and Comparative Examples 1-4 are statistically analyzed, as shown in the following Table 1.
[0043] Table 1 Test results of comparative examples 1-4
[0044] It can be seen from Table 1 that: 1) When propargyl alcohol is in excess, the yield of propargyl glycidyl ether is not much different from that when epichlorohydrin is in excess, but the price of propargyl alcohol is 5 times that of epichlorohydrin, and propargyl alcohol is a highly toxic substance, and the recovery process is risky, so epichlorohydrin is selected in excess. 2) When the activated clay is replaced with the phase transfer catalyst tetrabutylammonium bromide, the product yield decreases, indicating that the catalytic efficiency of activated clay is higher than that of the traditional phase transfer catalyst tetrabutylammonium bromide. 3) When the reaction temperature is increased to 55°C, the product yield decreases slightly. The reason is that the temperature increase leads to the occurrence of side reactions, so the reaction temperature needs to be strictly controlled. 4) The amount of alkali solution is adjusted to 225g, and the product yield decreases significantly. The reason is that the alkali solution is reduced, the reaction is not sufficient, and the amount of propargyl glycidyl ether generated is reduced.
[0045] Combined with the results in Table 1 above, it can be seen that through a large number of experimental explorations by the applicant, in the system of the present application, the molar ratio of propargyl alcohol to epichlorohydrin is 1:1.1, the activated clay is 5% of the mass of propargyl alcohol, the molar ratio of propargyl alcohol to alkali is 1:1.1, and the reaction temperature is 35-45°C, which can greatly improve the yield of the product to 91%-94% and the effective content of the product to 99.12%. The activated clay catalyst can be reused at least 10 times without environmental pollution.
[0046] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and the embodiments having the same structure as the technical idea and exerting the same effect within the scope of the technical solution of the present application are all included in the technical scope of the present application. In addition, without departing from the scope of the main purpose of the present application, various modifications that can be thought of by those skilled in the art to the embodiments and other methods of combining some of the constituent elements in the embodiments are also included in the scope of the present application.
Claims
1. A method for preparing high-purity propargyl glycidyl ether, characterized in that: The steps include: At 25-75° C., propargyl alcohol, epichlorohydrin and a catalyst are mixed and an alkali solution is added dropwise to react to obtain a mixed solution; The mixed solution is dissolved in water and filtered, the catalyst in the precipitate is recovered, and the liquid is layered to obtain a crude product of propynyl glycidyl ether; The crude propargyl glycidyl ether is distilled to obtain high-purity propargyl glycidyl ether.
2. The method for preparing high-purity propargyl glycidyl ether according to claim 1, characterized in that: The catalyst is activated clay.
3. The method for preparing high-purity propargyl glycidyl ether according to claim 2, characterized in that: During the preparation of the mixed solution, the conditions for adding the alkali solution are: the dropping temperature is 35 to 45° C., and the dropping time is 4 to 8 h.
4. The method for preparing high-purity propargyl glycidyl ether according to claim 3, characterized in that: During the preparation of the mixed solution, after the alkaline solution is added, the reaction is continued at 35-45° C. for 1.0-2.0 h.
5. The method for preparing high-purity propargyl glycidyl ether according to claim 2, characterized in that: The molar ratio of the propargyl alcohol to epichlorohydrin is 1:1 to 1:
10.
6. The method for preparing high-purity propargyl glycidyl ether according to claim 2, characterized in that: The mass ratio of the activated clay to propargyl alcohol is (0.01-0.1):
1.
7. The method for preparing high-purity propargyl glycidyl ether according to claim 2, characterized in that: The mixed solution is dissolved in water and filtered while hot, and the activated clay in the precipitate is recovered and reused for the preparation of subsequent mixed solutions.
8. The method for preparing high-purity propargyl glycidyl ether according to claim 2, characterized in that: The activated clay can be reused 1 to 20 times.
9. The method for preparing high-purity propargyl glycidyl ether according to claim 1, characterized in that: The alkali solution is any one of a sodium hydroxide solution or a potassium hydroxide solution or a mixture of the two.
10. The method for preparing high-purity propargyl glycidyl ether according to claim 1, characterized in that: The distillation conditions are: distillation temperature is 80-90°C, vacuum degree is -0.095-0.098MPa.