CN112250646B - Process for preparing alkyl glycidyl ethers - Google Patents
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- CN112250646B CN112250646B CN202011086910.8A CN202011086910A CN112250646B CN 112250646 B CN112250646 B CN 112250646B CN 202011086910 A CN202011086910 A CN 202011086910A CN 112250646 B CN112250646 B CN 112250646B
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- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
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Abstract
The invention provides an alkyl groupA method for preparing glycidyl ether. The preparation method of alkyl glycidyl ether comprises the following continuous flow substitution reaction is carried out on alkyl alcohol and epoxy halogenated propane in a micro-channel reactor, so as to obtain alkyl glycidyl ether; wherein the alkyl alcohol comprises a compound C shown in a formula I n H 2n+1 Mixing one or more of OH, wherein n in the formula I is 12-14; the epoxy halogenated propane has a structure shown in a formula II
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of alkyl glycidyl ether.
Background
UV-400 is a liquid ultraviolet absorber with excellent performance, is mainly used for high-performance paint and automobile paint, and has the following structure:
UV-400 was first developed successfully by Ciba, two starting materials for its synthesis, one of which was 4, 6-bis (2, 4-xylyl) -2- (2, 4-dihydroxyphenyl) -1,3, 5-triazine and the other was a mixed long carbon chain alkyl glycidyl ether, C 12 -C 14 An alkyl glycidyl ether group, wherein the alkyl glycidyl ether group,the UV-400 synthesis route is as follows:
therefore, it is desired to industrially produce UV absorber UV-400, C 12 -C 14 The technology for producing alkyl glycidyl ethers must be overcome.
C reported so far 12 -C 14 The synthesis of alkyl glycidyl ethers is less, as reported in patent CN101440074 as C 12 -C 14 The synthesis process of alkyl glycidyl ether includes the steps of using two kinds of Lewis acid as catalyst, boron trifluoride diethyl etherate and one of aluminium trichloride, tin tetrachloride and zinc chloride. However, the use of two Lewis acids results in a high catalytic cost, a high difficulty in post-treatment, a high toxicity of boron trifluoride, and a starting alcohol content of about 2.5% in the final product. Whereas the UV400 product is for C 12 -C 14 The purity of the alkyl glycidyl ether is required to be more than 99%, so that the synthesis method of the glycidyl ether is not suitable for C 12 -C 14 Actual production of alkyl glycidyl ethers.
Other methods of preparing alkyl glycidyl ethers have also been reported in the literature, such as: liu Shuang et al report a synthetic method of n-neo-glycidyl ether (fine and specialty chemicals, 2010, 18 (9): 24-27) using tetrabutylammonium bromide (TBAB) as a phase transfer catalyst and toluene as a solvent, but the purity of the prepared glycidyl ether is only 87%; the patent CN101704730 discloses a preparation method of five alkyl glycidyl ethers, wherein fluoboric acid is used as a catalyst, and the yield of the prepared glycidyl ether is only 53-78%; patent CN102971450 discloses a process for the preparation of alkyl glycidyl ethers, which uses ion exchange membranes to remove sodium chloride generated during the reaction and requires the application of an electric current to the ion exchange membranes during operation, which makes the process difficult to implement on a large scale.
Therefore, the problems of low product purity, low yield and the like commonly exist in the preparation of the existing alkyl glycidyl ether, especially the mixed long carbon chain alkyl glycidyl ether.
Disclosure of Invention
The invention mainly aims to provide a preparation method of alkyl glycidyl ether, which aims to solve the problems of low purity and low yield in the preparation of alkyl glycidyl ether in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a process for producing an alkyl glycidyl ether, characterized in that an alkyl alcohol and epihalohydrin are subjected to the following continuous flow substitution reaction in a microchannel reactor to obtain the alkyl glycidyl ether;
wherein the alkyl alcohol comprises a mixture of one or more compounds shown in a formula I, and n in the formula I is 12-14; the epoxy halopropane has a structure shown in formula II, and X in formula II is a halogen atom.
Further, the alkyl alcohol is a mixture of compounds having n of 12 to 14 in formula I, and the epihalohydrin is epichlorohydrin.
Further, the continuous flow substitution reaction is carried out in the presence of a catalyst and a liquid base; preferably, the catalyst is selected from one or more of tetrabutylammonium bromide, ethyltriphenylphosphine bromide and ethyltriphenylphosphine iodide; preferably, the liquid base is selected from aqueous solutions of sodium hydroxide.
Further, the preparation method comprises the following steps: mixing alkyl alcohol and epoxy halopropane to form a first raw material liquid; mixing a catalyst with liquid alkali to form a second raw material liquid; and (3) feeding the first raw material liquid and the second raw material liquid into a micro-channel reactor to perform continuous flow substitution reaction to obtain the alkyl glycidyl ether.
Further, the process of continuous flow substitution reaction comprises: continuously feeding the first raw material and the second raw material into a microchannel reactor for substitution reaction, and continuously discharging a substitution product obtained by the reaction out of the microchannel reactor; purifying the substituted product to obtain the alkyl glycidyl ether.
Further, in the continuous flow substitution reaction process, the feeding speeds of the first raw material and the second raw material are respectively and independently selected from 10-30 ml/min; preferably, the ratio of the feed rates of the first feedstock to the second feedstock is 1 (1 to 1.5).
Further, the retention time of the total material of the first material liquid and the second material liquid in the microchannel reactor is 1-5 min.
Further, the molar ratio between the alkyl alcohol and the epihalohydrin is 1 (1-1.5); preferably, the molar ratio between the alkali in the liquid alkali and the catalyst is 1 (0.01-0.05); preferably, the molar ratio of alkyl alcohol to catalyst is 1 (0.03-0.3).
Further, the temperature of the continuous flow substitution reaction is 50-70 ℃.
Further, the step of purifying the substitution product comprises: standing and layering the substituted product to obtain an organic phase; the organic phase was distilled under reduced pressure to obtain alkyl glycidyl ether.
The invention provides a preparation method of alkyl glycidyl ether, which is to carry out the following continuous flow substitution reaction on alkyl alcohol and epoxy halogenated propane in a micro-channel reactor to obtain the alkyl glycidyl ether. The microchannel reactor is adopted to prepare the alkyl glycidyl ether, and the heat exchange area is large, so that the thermal effect of the reaction is controllable, and the safety of the reaction can be effectively improved. Meanwhile, continuous flow substitution reaction is carried out in the microchannel reactor, no back mixing exists in the reaction process, and the alkyl glycidyl ether generated in the reaction process can be timely discharged from the reactor, so that the occurrence probability of side reaction can be effectively reduced, the subsequent post-treatment process is simplified, and the product purity is improved. In addition, by adopting the micro-channel reactor, alkyl alcohol and epoxy halogenated propane can be more fully and closely contacted in a reaction channel, so that the substitution reaction has higher efficiency and conversion rate, and the yield of a target product is relatively higher.
In a word, the invention effectively solves the problems of poor reaction safety, more byproducts and incapability of considering both product yield and purity in the preparation of the alkyl glycidyl ether in the prior art, and the preparation method provided by the invention has the advantages of simple operation process and high product purity, is a high-efficiency, safe and environment-friendly process route, and is suitable for industrial production.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As described in the background section, the prior art is low in purity and yield when preparing alkyl glycidyl ethers.
In order to solve the problems, the invention provides a preparation method of alkyl glycidyl ether, which comprises the following continuous flow substitution reaction of alkyl alcohol and epoxy halopropane in a micro-channel reactor to obtain alkyl glycidyl ether;
wherein the alkyl alcohol comprises a mixture of one or more compounds shown in a formula I, and n in a formula II is 12-14; the epoxy halopropane has a structure shown in formula II, and X in formula II is a halogen atom.
The synthesis process of glycidyl ether is found to be accompanied by a large amount of heat release of reaction, the synthesis of mixed long carbon chain alkyl glycidyl ether is tested by a reaction calorimeter, the heat of reaction can reach 124KJ/mol (calculated by epichlorohydrin), and the adiabatic temperature rise exceeds 100K. When the heat exchange fails, the temperature of the reaction liquid can reach far more than the boiling points of the epichlorohydrin and the liquid alkali. Therefore, the synthesis reaction of the product has very high safety risk, and the heat exchange requirement of the reactor is extremely high. In addition, since the target product also carries an epoxy group, the group also reacts with the raw alcohol. Therefore, the glycidyl ether is prepared by adopting the traditional kettle-type reactor, and the product can be subjected to back mixing in the reaction kettle until the reaction is finished, so that a large amount of byproducts can be carried in the product, and a large pressure is brought to the later purification. The alkyl glycidyl ether is prepared by carrying out the following continuous flow substitution reaction on alkyl alcohol and epoxy halogenated propane in a micro-channel reactor. The microchannel reactor is adopted to prepare the alkyl glycidyl ether, and the heat exchange area is large, so that the thermal effect of the reaction is controllable, and the safety of the reaction can be effectively improved. Meanwhile, continuous flow substitution reaction is carried out in the microchannel reactor, no back mixing exists in the reaction process, and the alkyl glycidyl ether generated in the reaction process can be timely discharged from the reactor, so that the occurrence probability of side reaction can be effectively reduced, the subsequent post-treatment process is simplified, and the product purity is improved (the purity is up to more than 99 percent) on the one hand. In addition, by adopting the micro-channel reactor, alkyl alcohol and epoxy halogenated propane can be more fully and closely contacted in a reaction channel, so that the substitution reaction has higher efficiency and conversion rate, and the yield of a target product is relatively higher.
In a word, the invention effectively solves the problems of poor reaction safety, more byproducts and incapability of considering both product yield and purity in the preparation of the alkyl glycidyl ether in the prior art, and the preparation method provided by the invention has the advantages of simple operation process and high product purity, is a high-efficiency, safe and environment-friendly process route, and is suitable for industrial production.
It should be noted that, because of the size specificity of the reaction site, the microchannel reactor has strict requirements on the performance, the density of raw materials, the viscosity and the like of the reaction system, and not all glycidyl ethers are suitable for the preparation by using the microchannel reactor. The alkyl alcohol comprises a mixture of one or more of the compounds shown in the formula I, wherein n in the formula II is 12-14; the epoxy halopropane has a structure shown in formula II, and X in formula II is a halogen atom. With the alkyl alcohol and the epoxy halopropane, the reaction system is more suitable for continuous flow substitution reaction in a microchannel reactor.
The preparation method provided by the invention is suitable for preparing the alkyl glycidyl ether, and is more preferably applied to the preparation of the mixed long carbon chain alkyl glycidyl ether in consideration of the severity of heat release problem, byproduct problem and the like in the production process, namely, the alkyl alcohol is the mixture of compounds with n of 12-14 in the formula I, and the epoxy halopropane is epoxy chloropropane. In the preparation process of the mixed long carbon chain alkyl glycidyl ether, the requirement on the purity of the product is higher, and the requirement on the reaction condition is more severe because the alkyl alcohol in the raw materials is a mixture. The continuous flow substitution reaction of the mixed long carbon chain alkyl alcohol and the epoxy chloropropane is carried out by adopting the micro-channel reactor, so that the characteristics of strong heat control capability, high reaction efficiency, few byproducts and the like of the micro-channel reactor can be fully exerted, the mixed long carbon chain alkyl glycidyl ether with high purity (more than 99 percent) can be prepared more safely, more green and more efficiently, and the use requirement of UV400 can be met.
In a preferred embodiment, the continuous flow substitution reaction is carried out in the presence of a catalyst and a liquid base. The liquid alkali can timely remove small molecular acid byproducts in the substitution reaction process, and the substitution reaction is more efficient by matching with the action of the catalyst. Preferably, the catalyst is selected from one or more of tetrabutylammonium bromide, ethyltriphenylphosphine bromide and ethyltriphenylphosphine iodide; preferably, the liquid base is selected from aqueous solutions of sodium hydroxide. The reaction system formed by the catalyst and the liquid alkali and the alkyl alcohol and the epichlorohydrin is more matched with the micro-channel reactor in the aspects of viscosity, density and flow state, so that the continuous flow substitution reaction is more stable. In addition, the prices of the catalysts are relatively low, which is beneficial to reducing the production cost.
In order to make the continuous flow substitution reaction more efficient, in a preferred embodiment, the above-described preparation method comprises the steps of: mixing alkyl alcohol and epoxy halopropane to form a first raw material liquid; mixing a catalyst with liquid alkali to form a second raw material liquid; and (3) feeding the first raw material liquid and the second raw material liquid into a micro-channel reactor to perform continuous flow substitution reaction to obtain the alkyl glycidyl ether. Thus, the reaction monomers are mixed in advance, the catalytic gas is mixed and then introduced into the microchannel reactor for reaction, which is favorable for the full contact of the reaction raw materials, so that the reaction time is reduced as much as possible, and the higher yield is obtained under the condition of smaller retention time.
In the actual operation process, the first raw material liquid and the second raw material liquid can be respectively placed in the two liquid storage units, and then the two raw material liquids are respectively conveyed into the microchannel reactor for reaction through a liquid driving device such as a conveying pump. In order to make the reaction more stable, a flowmeter may be disposed on each of the conveying pipes so as to monitor the conveying speed of the raw material liquid.
In a preferred embodiment, the process of the continuous flow substitution reaction described above comprises: continuously feeding the first raw material and the second raw material into a microchannel reactor for substitution reaction, and continuously discharging a substitution product obtained by the reaction out of the microchannel reactor; purifying the substituted product to obtain the alkyl glycidyl ether. Thus, the reaction product is discharged in time and purified, the occurrence probability of side reaction is reduced, and the product purity is improved more favorably. The specific purification process can be of a type commonly used in the art, but as described above, the purification process can be effectively simplified because the alkyl glycidyl ether is prepared by the micro-channel reactor, and fewer byproducts are generated in the reaction product. In practice, the above purification steps preferably include: standing and layering the substituted product to obtain an organic phase; the organic phase was distilled under reduced pressure to obtain alkyl glycidyl ether. After standing and layering, the organic phase can also be washed by deionized water and then distilled under reduced pressure. The fraction at 180-190 ℃ can be collected in the vacuum distillation process, and the target product alkyl glycidyl ether is obtained.
In order to further improve the reaction efficiency and the product yield, the alkyl alcohol and the epoxy halopropane are more fully reacted, and in a preferred embodiment, the feeding speeds of the first raw material and the second raw material are respectively and independently selected from 10-30 ml/min in the process of continuous flow substitution reaction; preferably, the ratio of the feed rates of the first feedstock to the second feedstock is 1 (1 to 1.5).
In a preferred embodiment, the total material of the first and second feed solutions has a retention time in the microchannel reactor of from 1 to 5 minutes. The retention time is controlled within the range, which is more beneficial to the aspects of reaction efficiency, product purity and the like. Preferably, the temperature of the continuous flow substitution reaction is 50 to 70 ℃. In the actual operation process, the temperature of the micro-channel reactor can be raised to the reaction temperature in advance, and then the raw material liquid is introduced into the micro-channel reactor for reaction. For example, the hot oil can be introduced into the temperature control jacket of the microchannel reactor through the heat exchange system, and after the temperature of the hot oil outlet is stable, the conveying pipeline of the raw material liquid is opened, and the specific operation can be understood by those skilled in the art, and the details are not repeated here.
In a preferred embodiment, the molar ratio between alkyl alcohol and epihalohydrin is 1 (1 to 1.5); preferably, the molar ratio between the alkali in the liquid alkali and the catalyst is 1 (0.01-0.05); preferably, the molar ratio of alkyl alcohol to catalyst is 1 (0.03-0.3). The use amount relation of the raw materials is controlled within the range, so that the substitution reaction efficiency is improved, and the whole reaction system is more stable after the raw material liquid enters the microchannel reactor.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Example 1
In this example, a mixed long carbon chain alkyl glycidyl ether was prepared, specifically as follows:
196g (about 1.0 mol) of C are added at normal temperature (about 25 ℃) 12 -C 14 Adding long-chain mixed alkyl alcohol (commercially available) and 111g (1.2 mol) of epoxy chloropropane into a single-neck flask, magnetically stirring until materials are completely mixed to form a first raw material liquid; 48g (1.2 mol) NaOH, 300ml water and 11g (0.03 mol) ethyl triphenylphosphine bromide are added into a single-neck round-bottom flask, and the mixture is stirred magnetically until the mixture is completely mixed to form a second raw material liquid;
and opening a heat exchange system of the microchannel reactor, setting the temperature of hot oil to be 50 ℃, starting two feed pumps A and B after the temperature of the hot oil outlet of the microchannel reactor is 50+/-0.5 ℃, and conveying the first raw material liquid by the feed pump A and the second raw material liquid by the feed pump B. Wherein, the material conveying speed of the first raw material liquid and the second raw material liquid is 20ml/min, and the total material of the first raw material liquid and the second raw material liquid is kept for 3.2min in the microchannel reactor through 6 microchannel reaction modules (the volume of each module is 8ml, the modules are sequentially connected in series and the pore channels are folded and arranged), so as to carry out continuous flow substitution reaction, and continuous feeding and continuous discharging are carried out in the reaction process.
The reaction solution is received by a 1000ml four-mouth round bottom flask, the reaction solution is kept stand, the lower water phase is separated, a small amount of water is added, the water is washed once, the organic phase is distilled under reduced pressure, the fraction (2-3 mmHg) at 180-190 ℃ is collected, the product is colorless and slightly viscous liquid, the yield is 85%, and the gas chromatography content is 99.4%.
Product GCMS: c (C) 15 H 30 O 2 [M+]= 242.40 (C12 alkyl glycidyl ether), C 17 H 34 O 2 [M+]= 270.46 (C14 alkyl glycidyl ether), ion peaks, 111, 125, 139, 153, 171, 185, 227. Infrared spectral wavenumber (cm-1): 2955, 2919, 2865, 1466, 1384, 1248, 1103, 912, 839, 758.
Example 2
The difference from example 1 is that:
and opening a heat exchange system of the microchannel reactor, setting the temperature of hot oil to be 60 ℃ and the temperature of a hot oil outlet of the microchannel reactor to be 60+/-0.5 ℃, and starting two feeding pumps A and B, wherein the feeding pump A is used for conveying the first raw material liquid, and the feeding pump B is used for conveying the second raw material liquid. Wherein, the conveying speed of the first raw material liquid and the second raw material liquid is 20ml/min, the retention time of the materials is 1.2min, and the materials are continuously fed and continuously discharged.
The reaction solution is received by a 1000ml four-mouth round bottom flask, the reaction solution is kept stand, the lower water phase is separated, a small amount of water is added, the water is washed once, the organic phase is distilled under reduced pressure, the fraction (2-3 mmHg) at 180-190 ℃ is collected, the product is colorless and slightly viscous liquid, the yield is 83%, and the gas chromatography content is 99.6%.
Example 3
The difference from example 1 is that:
and opening a heat exchange system of the microchannel reactor, setting the temperature of hot oil to be 60 ℃ and the temperature of a hot oil outlet of the microchannel reactor to be 60+/-0.5 ℃, and starting two feeding pumps A and B, wherein the feeding pump A is used for conveying the first raw material liquid, and the feeding pump B is used for conveying the second raw material liquid. Wherein, the conveying speed of the first raw material liquid and the second raw material liquid is 15ml/min, the retention time of the materials is 1.6min, and the materials are continuously fed and continuously discharged.
A1000 ml four-neck round bottom flask is used for receiving the reaction liquid, the reaction liquid is kept stand, the lower water phase is separated, a small amount of water is added, the water is washed once, the organic phase is distilled under reduced pressure, the fraction (2-3 mmHg) at 180-190 ℃ is collected, the product is colorless and slightly viscous liquid, the yield is 86.6%, and the gas chromatography content is 99.7%.
Example 4
The difference from example 1 is that:
196g (about 1.0 mol) of C are added at normal temperature (about 25 ℃) 12 -C 14 Adding long-chain mixed alkyl alcohol and 139g (1.5 mol) epichlorohydrin into a single-neck flask, and magnetically stirring until the materials are completely mixed to form a first raw material liquid; 48g (1.2 mol) NaOH, 300ml water and 9.67g (0.03 mol) tetrabutylammonium bromide are added into a single-neck round-bottom flask and are stirred electromagnetically until being mixed completely, so as to form a second raw material liquid;
and opening a heat exchange system of the microchannel reactor, setting the temperature of hot oil to be 60 ℃ and the temperature of a hot oil outlet of the microchannel reactor to be 60+/-0.5 ℃, and starting two feeding pumps A and B, wherein the feeding pump A is used for conveying the first raw material liquid, and the feeding pump B is used for conveying the second raw material liquid. Wherein, the conveying speed of the first raw material liquid and the second raw material liquid is 15ml/min, the retention time of the materials is 1.6min, and the materials are continuously fed and continuously discharged.
The reaction solution is received by a 1000ml four-mouth round bottom flask, the reaction solution is kept stand, the lower water phase is separated, a small amount of water is added, the water is washed once, the organic phase is distilled under reduced pressure, the fraction (2-3 mmHg) at 180-190 ℃ is collected, the product is colorless and slightly viscous liquid, the yield is 87.4%, and the gas chromatography content is 99.5%.
Example 5
The difference from example 1 is that:
196g (about 1.0 mol) of C are added at normal temperature (about 25 ℃) 12 -C 14 Adding long-chain mixed alkyl alcohol (commercially available) and 93g (1 mol) of epichlorohydrin into a single-neck flask, and magnetically stirring until the materials are completely mixed to form a first raw material liquid; 240g (6 mol) NaOH, 300ml water and 110g (0.3 mol) ethyl triphenylphosphine bromide are added into a single-neck round-bottom flask, and the mixture is stirred magnetically until the mixture is completely mixed to form a second raw material liquid;
and opening a heat exchange system of the microchannel reactor, setting the temperature of hot oil to be 60 ℃ and the temperature of a hot oil outlet of the microchannel reactor to be 60+/-0.5 ℃, and starting two feeding pumps A and B, wherein the feeding pump A is used for conveying the first raw material liquid, and the feeding pump B is used for conveying the second raw material liquid. Wherein, the conveying speed of the first raw material liquid and the second raw material liquid is 30ml/min, the retention time of the materials is 1.6min, and the materials are continuously fed and continuously discharged.
A1000 ml four-neck round bottom flask is used for receiving the reaction liquid, the reaction liquid is kept stand, the lower water phase is separated, a small amount of water is added, the water is washed once, the organic phase is distilled under reduced pressure, the fraction (2-3 mmHg) at 180-190 ℃ is collected, the product is colorless and slightly viscous liquid, the yield is 85.6%, and the gas chromatography content is 99.2%.
Example 6
The difference from example 1 is that:
196g (about 1.0 mol) of C are added at normal temperature (about 25 ℃) 12 -C 14 Adding long-chain mixed alkyl alcohol (commercially available) and 111g (1.2 mol) of epoxy chloropropane into a single-neck flask, magnetically stirring until materials are completely mixed to form a first raw material liquid; 120g (3 mol) NaOH, 300ml water and 11g (0.03 mol) ethyl triphenylphosphine bromide are added into a single-neck round-bottom flask, and the mixture is stirred magnetically until the mixture is completely mixed to form a second raw material liquid;
and opening a heat exchange system of the microchannel reactor, setting the temperature of hot oil to be 60 ℃ and the temperature of a hot oil outlet of the microchannel reactor to be 60+/-0.5 ℃, and starting two feeding pumps A and B, wherein the feeding pump A is used for conveying the first raw material liquid, and the feeding pump B is used for conveying the second raw material liquid. Wherein, the conveying speed of the first raw material liquid and the second raw material liquid is 30ml/min, the retention time of the materials is 1.6min, and the materials are continuously fed and continuously discharged.
A1000 ml four-neck round bottom flask is used for receiving the reaction liquid, the reaction liquid is kept stand, the lower water phase is separated, a small amount of water is added, the water is washed once, the organic phase is distilled under reduced pressure, the fraction (2-3 mmHg) at 180-190 ℃ is collected, the product is colorless and slightly viscous liquid, the yield is 83.5%, and the gas chromatography content is 99.3%.
Comparative example 1
196g (about 1.0 m) ofol)C 12 -C 14 Long-chain mixed alkyl alcohol, 9.67g (0.03 mol) tetrabutylammonium bromide, 48g (1.2 mol) NaOH and 300ml water are added into a 1000ml four-neck flask, 139g (1.5 mol) epichlorohydrin is added dropwise, the time is 2 hours, the temperature is kept for 1 hour at 40 ℃ after the dropwise addition, the temperature is raised to 60 ℃ after the dropwise addition, the temperature is kept for 3 hours, and the reaction is stopped. Separating the liquid after the reaction is finished, separating the lower water phase, washing the organic phase with water for 3 times until the organic phase is neutral, then carrying out reduced pressure distillation, collecting 180-190 ℃ fractions (2-3 mmHg), wherein the product is colorless and slightly viscous liquid, the yield is 67.4%, and the gas chromatography content is 99.4%.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The preparation method of the alkyl glycidyl ether is characterized in that alkyl alcohol and epoxy halopropane are subjected to the following continuous flow substitution reaction in a micro-channel reactor to obtain the alkyl glycidyl ether;
I II
wherein the alkyl alcohol comprises a mixture of one or more compounds shown in a formula I, and n in the formula I is 12-14; the epoxy halopropane has a structure shown in a formula II, and X in the formula II is a halogen atom; the continuous flow substitution reaction is carried out in the presence of a catalyst and a liquid base; the catalyst is selected from one or more of ethyl triphenylphosphine bromide and ethyl triphenylphosphine iodide;
the preparation method comprises the following steps:
mixing the alkyl alcohol with the epoxy halopropane to form a first raw material liquid;
mixing the catalyst with the liquid alkali to form a second raw material liquid;
feeding the first raw material liquid and the second raw material liquid into the microchannel reactor to perform the continuous flow substitution reaction to obtain the alkyl glycidyl ether;
in the continuous flow substitution reaction process, the feeding speeds of the first raw material and the second raw material are respectively and independently selected from 10-30 ml/min; the ratio of the feeding speed of the first raw material to the feeding speed of the second raw material is 1 (1-1.5); the retention time of the total material of the first raw material liquid and the second raw material liquid in the microchannel reactor is 1-3.2 min.
2. The method for producing an alkyl glycidyl ether according to claim 1, wherein the alkyl alcohol is a mixture of compounds having n of 12 to 14 in formula I, and the epihalohydrin is epichlorohydrin.
3. The process for the preparation of alkyl glycidyl ethers according to claim 1 or 2 wherein the liquid base is selected from aqueous solutions of sodium hydroxide.
4. The method of preparing an alkyl glycidyl ether according to claim 1 wherein the continuous flow substitution reaction comprises:
continuously feeding the first raw material and the second raw material into the microchannel reactor for substitution reaction, and continuously discharging a substitution product obtained by the reaction out of the microchannel reactor;
purifying the substituted product to obtain the alkyl glycidyl ether.
5. The method for producing an alkyl glycidyl ether according to claim 1, wherein a molar ratio between the alkyl alcohol and the epihalohydrin is 1 (1 to 1.5);
the molar ratio between the alkali in the liquid alkali and the catalyst is 1 (0.01-0.05);
the molar ratio of the alkyl alcohol to the catalyst is 1 (0.03-0.3).
6. The method for preparing alkyl glycidyl ether according to claim 1 or 2, wherein the temperature of the continuous flow substitution reaction is 50-70 ℃.
7. The method for producing an alkyl glycidyl ether according to claim 4, wherein the step of purifying the substituted product comprises:
standing and layering the substituted product to obtain an organic phase;
and carrying out reduced pressure distillation on the organic phase to obtain the alkyl glycidyl ether.
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| CN115124492A (en) * | 2022-07-29 | 2022-09-30 | 上海华谊树脂有限公司 | Process for synthesizing tetraglycidyl amine epoxy resin by continuous method |
| CN115819327A (en) * | 2022-11-04 | 2023-03-21 | 天津利安隆新材料股份有限公司 | Hindered amine compound, preparation method and application thereof |
| CN116063248A (en) * | 2022-12-07 | 2023-05-05 | 山东尚正新材料科技股份有限公司 | Method for continuously producing biomass glycidyl ether |
| CN115947702B (en) * | 2022-12-12 | 2024-04-12 | 江苏扬农锦湖化工有限公司 | Preparation method of octyl glycidyl ether |
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