CN112250646A - Process for preparing alkyl glycidyl ethers - Google Patents
Process for preparing alkyl glycidyl ethers Download PDFInfo
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- CN112250646A CN112250646A CN202011086910.8A CN202011086910A CN112250646A CN 112250646 A CN112250646 A CN 112250646A CN 202011086910 A CN202011086910 A CN 202011086910A CN 112250646 A CN112250646 A CN 112250646A
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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 a preparation method of alkyl glycidyl ether. The preparation method of alkyl glycidyl ether comprises the following continuous flow substitution reaction of alkyl alcohol and epoxy halogenated propane in a microchannel reactor to obtain alkyl glycidyl ether; wherein the alkyl alcohol comprises a compound C represented by formula InH2n+1One or more of OH, and n in the formula I is 12-14; the epoxy halogenated propane has a structure shown in formula II
Description
Technical Field
The invention relates to the technical field of organic synthesis, and particularly relates 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 coatings and automobile paints, and has the following structure:
UV-400 was first developed successfully for Ciba, and two raw materials were used 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, i.e., C12-C14The synthesis route of alkyl glycidyl ether and UV-400 is as follows:
therefore, it is desired to industrially produce the ultraviolet absorber UV-400, C12-C14The production technology of alkyl glycidyl ethers must be overcome.
C reported so far12-C14Alkyl glycidyl ethers have a few synthesis methods, for example, a C is reported in patent CN10144007412-C14The synthesis process of alkyl glycidyl ether includes the first two kinds of Lewis acid as catalyst, and the second one of boron trifluoride ether and aluminum trichloride, tin tetrachloride and zinc chloride. However, the use of two lewis acids results in higher catalytic costs, greater difficulty in post-treatment, greater toxicity of boron trifluoride, and a starting alcohol content of about 2.5% in the final product. And UV400 products for C12-C14The purity requirement of alkyl glycidyl ether is more than 99%, therefore, the synthesis method of the glycidyl ether is not suitable for C12-C14Practice of alkyl glycidyl ethersAnd (4) production.
Other processes for the preparation of alkyl glycidyl ethers have also been reported in some literature, such as: liu Shuang et al reported a synthesis method of n-neoyl 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 was only 87%; in patent CN101704730, a preparation method of five alkyl glycidyl ethers is disclosed, wherein fluoroboric acid is used as a catalyst, and the yield of the prepared glycidyl ethers is only 53-78%; patent CN102971450 discloses a process for preparing alkyl glycidyl ether, which uses an ion exchange membrane to remove sodium chloride generated in the reaction process, and needs to apply current to the ion exchange membrane during operation, which makes the process difficult to implement on a large scale.
It can be seen that the problems of low product purity, low yield and the like generally exist in the preparation of the current 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 objects, according to one aspect of the present invention, there is provided a method for producing an alkyl glycidyl ether, characterized by subjecting an alkyl alcohol and a halogenated propylene oxide to the following continuous flow substitution reaction in a microchannel reactor to obtain an alkyl glycidyl ether;
wherein the alkyl alcohol comprises one or more of compounds shown in formula I, and n in the formula I is 12-14; the epoxy halogenated propane has a structure shown in a formula II, and X in the formula II is a halogen atom.
Further, the alkyl alcohol is a mixture of compounds with n of 12-14 in the formula I, and the epoxy halogenated propane is epoxy chloropropane.
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, ethyltriphenylphosphonium bromide and ethyltriphenylphosphonium iodide; preferably, the liquid alkali is selected from aqueous solutions of sodium hydroxide.
Further, the preparation method comprises the following steps: mixing an alkyl alcohol with a halogenated propylene oxide to form a first feed solution; mixing a catalyst with liquid alkali to form a second raw material liquid; and feeding the first raw material liquid and the second raw material liquid into a microchannel reactor to carry out continuous flow substitution reaction to obtain the alkyl glycidyl ether.
Further, the process of continuous flow substitution reaction includes: 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 substitution product to obtain the alkyl glycidyl ether.
Further, in the process of continuous flow substitution reaction, 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 feeding speed of the first raw material to the feeding speed of the second raw material is 1 (1-1.5).
Further, the retention time of the total material of the first raw material liquid and the second raw material liquid in the microchannel reactor is 1-5 min.
Further, the molar ratio of the alkyl alcohol to the halogenated propylene oxide is 1 (1-1.5); preferably, the molar ratio of the alkali in the liquid alkali to the catalyst is 1 (0.01-0.05); preferably, the molar ratio of the alkyl alcohol to the 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 substitution product to obtain an organic phase; and distilling the organic phase under reduced pressure to obtain the alkyl glycidyl ether.
The invention provides a preparation method of alkyl glycidyl ether, which comprises the following continuous flow substitution reaction of alkyl alcohol and epoxy halogenated propane in a microchannel reactor to obtain the alkyl glycidyl ether. The alkyl glycidyl ether is prepared by adopting the microchannel reactor, and the safety of the reaction can be effectively improved because the heat exchange area is large and the heat effect of the reaction is controllable. Meanwhile, continuous flow substitution reaction is carried out in the microchannel reactor, back mixing does not exist in the reaction process, and alkyl glycidyl ether generated in the reaction process can be discharged out of the reactor in time, 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 microchannel reactor, the alkyl alcohol and the halogenated propylene oxide can be in more sufficient and close contact in the reaction channel, so that the substitution reaction has higher efficiency and conversion rate, and the yield of the target product is relatively higher.
In a word, the preparation method effectively solves the problems of poor reaction safety, more byproducts and incapability of considering both product yield and purity in the process of preparing alkyl glycidyl ether in the prior art, has simple operation process and high product purity, is an efficient, safe and environment-friendly process route, and is suitable for industrial production.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background section, the alkyl glycidyl ethers prepared in the prior art have a low purity and a low yield.
In order to solve the problems, the invention provides a preparation method of alkyl glycidyl ether, which comprises the following steps of carrying out continuous flow substitution reaction on alkyl alcohol and halogenated propylene oxide in a microchannel reactor to obtain the alkyl glycidyl ether;
wherein the alkyl alcohol comprises one or more of compounds shown in formula I, and n in formula II is 12-14; the epoxy halogenated propane has a structure shown in a formula II, and X in the formula II is a halogen atom.
Research shows that the synthesis process of the glycidyl ether is accompanied by a great deal of reaction heat release, and the reaction heat can reach 124KJ/mol (calculated by epichlorohydrin) and the adiabatic temperature rise exceeds 100K when the synthesis process is tested by a reaction calorimeter and is used for synthesizing the mixed long-carbon chain alkyl glycidyl ether. When the heat exchange is invalid, the temperature which can be reached by the reaction liquid far exceeds the boiling point of the epichlorohydrin and the liquid alkali. Therefore, the synthesis reaction of the product has very high safety risk and extremely high heat exchange requirement on the reactor. In addition, since the target product also carries an epoxy group, the group is also reacted with the raw alcohol. Therefore, the glycidyl ether is prepared by adopting the traditional kettle type reactor, and the product is always back-mixed in the reaction kettle and can not be post-treated 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 the following continuous flow substitution reaction of alkyl alcohol and epoxy halogenated propane in a microchannel reactor. The alkyl glycidyl ether is prepared by adopting the microchannel reactor, and the safety of the reaction can be effectively improved because the heat exchange area is large and the heat effect of the reaction is controllable. Meanwhile, continuous flow substitution reaction is carried out in the microchannel reactor, back mixing does not exist in the reaction process, and alkyl glycidyl ether generated in the reaction process can be discharged out of the reactor in time, so that the occurrence probability of side reaction can be effectively reduced, the subsequent post-treatment process is simplified, and the product purity (the purity is up to more than 99%) is improved. In addition, by adopting the microchannel reactor, the alkyl alcohol and the halogenated propylene oxide can be in more sufficient and close contact in the reaction channel, so that the substitution reaction has higher efficiency and conversion rate, and the yield of the target product is relatively higher.
In a word, the preparation method effectively solves the problems of poor reaction safety, more byproducts and incapability of considering both product yield and purity in the process of preparing alkyl glycidyl ether in the prior art, has simple operation process and high product purity, is an efficient, safe and environment-friendly process route, and is suitable for industrial production.
It should be noted here that the microchannel reactor has strict requirements on the properties of the reaction system, the density of raw materials, the viscosity, and the like due to the special size of the reaction site, and not all glycidyl ethers are suitable for preparation by the microchannel reactor. The alkyl alcohol comprises one or more of compounds shown in a formula I, and n in a formula II is 12-14; the epoxy halogenated propane has a structure shown in a formula II, and X in the formula II is a halogen atom. By adopting the alkyl alcohol and the epoxy halogenated propane, the reaction system is more suitable for carrying out continuous flow substitution reaction in a microchannel reactor.
The preparation method provided by the invention is suitable for preparing the alkyl glycidyl ether, and certainly, in consideration of the severity of heat release problem, byproduct problem and the like in the production process, the method is more preferably applied to the preparation of mixed long-carbon chain alkyl glycidyl ether, namely, alkyl alcohol is the mixture of compounds with n of 12-14 in formula I, and epoxy halogenated propane is epoxy chloropropane. In the preparation process of the mixed long-carbon chain alkyl glycidyl ether, the requirement on the product purity is higher, and the requirement on the reaction condition is more severe because the alkyl alcohol in the raw materials is a mixture. And the continuous flow substitution reaction of the mixed long-carbon chain alkyl alcohol and the epoxy chloropropane is carried out by adopting the microchannel reactor, so that the characteristics of strong heat control capability, high reaction efficiency, few byproducts and the like of the microchannel reactor can be more fully exerted, the mixed long-carbon chain alkyl glycidyl ether with high purity (more than 99 percent) can be prepared more safely, greener 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 caustic soda can remove the micromolecule acid by-product in the process of the substitution reaction in time, 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, ethyltriphenylphosphonium bromide and ethyltriphenylphosphonium iodide; preferably, the liquid alkali 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 microchannel reactor in the aspects of viscosity, density and flow state, so that the continuous flow substitution reaction is more stable. Besides, the price of the catalysts is 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 preparation method comprises the steps of: mixing an alkyl alcohol with a halogenated propylene oxide to form a first feed solution; mixing a catalyst with liquid alkali to form a second raw material liquid; and feeding the first raw material liquid and the second raw material liquid into a microchannel reactor to carry out continuous flow substitution reaction to obtain the alkyl glycidyl ether. Therefore, the reaction monomers are mixed in advance, the catalytic gases are mixed, and then the mixture is introduced into the microchannel reactor for reaction, so that the full contact of all reaction raw materials is facilitated, the reaction time is shortened as much as possible, and higher yield is obtained under shorter retention time.
In practical operation, 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 to the microchannel reactor for reaction through a liquid driving device, such as a conveying pump. In order to make the reaction more stable, a flow meter may be provided on each of the transfer lines to monitor the transfer rate of the raw material liquid.
In a preferred embodiment, the process of the 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 substitution product to obtain the alkyl glycidyl ether. Therefore, the reaction product is timely discharged and purified, the occurrence probability of side reaction is reduced, and the product purity is improved. The specific purification process can be the type commonly used in the art, but as mentioned above, since the present invention adopts the microchannel reactor to prepare the alkyl glycidyl ether, the by-products in the reaction product are less, and the purification process can be effectively simplified. In practice, it is preferable that the purification step comprises: standing and layering the substitution product to obtain an organic phase; and distilling the organic phase under reduced pressure to obtain the alkyl glycidyl ether. After standing and layering, the organic phase can also be washed by deionized water and then distilled under reduced pressure. Fractions at about 180-190 ℃ can be collected in the process of reduced pressure distillation, and the fractions are the target product alkyl glycidyl ether.
In order to further improve the reaction efficiency and the product yield and enable the alkyl alcohol and the halogenated propylene oxide to react more fully, in a preferred embodiment, the feeding speeds of the first raw material and the second raw material are respectively and independently selected from 10 to 30ml/min during the continuous flow substitution reaction; preferably, 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).
In a preferred embodiment, the total retention time of the first raw material liquid and the second raw material liquid in the microchannel reactor is 1-5 min. The retention time is controlled within the range, so that the reaction efficiency, the product purity and the like are better considered. Preferably, the temperature of the continuous flow substitution reaction is 50-70 ℃. In the actual operation process, the temperature of the microchannel reactor can be raised to the reaction temperature in advance, and then the raw material liquid is introduced into the microchannel reactor for reaction. For example, 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 stabilized, the conveying pipeline of the raw material liquid is opened.
In a preferred embodiment, the molar ratio between the alkyl alcohol and the epihalohydrin is 1 (1-1.5); preferably, the molar ratio of the alkali in the liquid alkali to the catalyst is 1 (0.01-0.05); preferably, the molar ratio of the alkyl alcohol to the catalyst is 1 (0.03-0.3). The dosage relation of all raw materials is controlled in the range, so that the efficiency of substitution reaction is improved, and the whole reaction system is more stable after raw material liquid enters the microchannel reactor.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
In this example, a mixed long carbon chain alkyl glycidyl ether was prepared by the following procedure:
196g (about 1.0mol) of C was charged at room temperature (about 25 ℃ C.)12-C14Adding long-chain mixed alkyl alcohol (commercially available) and 111g (1.2mol) of epichlorohydrin into a single-neck flask, and magnetically stirring until the materials are completely mixed to form a first raw material solution; adding 48g (1.2mol) of NaOH, 300ml of water and 11g (0.03mol) of ethyltriphenylphosphonium bromide into a single-neck round-bottom flask, and electromagnetically stirring until the materials are completely mixed to form a second raw material liquid;
and (3) opening a heat exchange system of the microchannel reactor, setting the temperature of hot oil to be 50 ℃, starting two feeding pumps A and B when the temperature of a hot oil outlet of the microchannel reactor is 50 +/-0.5 ℃, wherein the feeding pump A conveys a first raw material liquid, and the feeding pump B conveys a second raw material liquid. The conveying speeds of the first raw material liquid and the second raw material liquid are both 20ml/min, the continuous flow substitution reaction is carried out after the first raw material liquid and the second raw material liquid pass through 6 microchannel reaction modules (the volume of each module is 8ml, the modules are sequentially connected in series, and pore channels are arranged in a folding manner), the retention time of the total materials of the first raw material liquid and the second raw material liquid in a microchannel reactor is 3.2min, 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, then the reaction solution is kept stand, the lower water phase is separated out, a small amount of water is added, the water is washed once, the organic phase is distilled under reduced pressure, 180-DEG C190 ℃ fraction (2-3mmHg) is collected, the product is colorless and slightly viscous liquid, the yield is 85 percent, and the content of gas chromatography is 99.4 percent.
And (3) a product GCMS: c15H30O2[M+]242.40(C12 alkyl glycidyl ether), C17H34O2[M+]270.46(C14 alkyl glycidyl ether), ion peak, 111, 125, 139, 153, 171, 185, 227. Infrared spectrum wave number (cm-1): 2955, 2919, 2865, 1466, 1384, 1248, 1103, 912, 839, 758.
Example 2
The difference from the embodiment 1 is that:
and (3) opening a heat exchange system of the microchannel reactor, setting the temperature of hot oil to be 60 ℃ to 60 +/-0.5 ℃ at a hot oil outlet of the microchannel reactor, starting two feeding pumps A and B, wherein the feeding pump A conveys a first raw material liquid, and the feeding pump B conveys a second raw material liquid. Wherein, the material conveying speed of the first raw material liquid and the second raw material liquid is 20ml/min, the retention time of the material is 1.2min, and the continuous feeding and the continuous discharging are carried out.
The reaction solution is received by a 1000ml four-mouth round-bottom flask, then the reaction solution is kept stand, the lower water phase is separated, a small amount of water is added, the reaction solution is washed once, the organic phase is distilled under reduced pressure, 180-DEG C190-DEG C fraction (2-3mmHg) is collected, the product is colorless and slightly viscous liquid, the yield is 83 percent, and the content of a gas chromatography is 99.6 percent.
Example 3
The difference from the embodiment 1 is that:
and (3) opening a heat exchange system of the microchannel reactor, setting the temperature of hot oil to be 60 ℃ to 60 +/-0.5 ℃ at a hot oil outlet of the microchannel reactor, starting two feeding pumps A and B, wherein the feeding pump A conveys a first raw material liquid, and the feeding pump B conveys a second raw material liquid. Wherein, the material conveying speed of the first raw material liquid and the second raw material liquid is 15ml/min, the retention time of the material is 1.6min, and the continuous feeding and the continuous discharging are carried out.
The reaction solution was received by a 1000ml four-necked round-bottomed flask, then the reaction solution was allowed to stand, the lower aqueous phase was separated, a small amount of water was added, washing was conducted once, the organic phase was distilled under reduced pressure, 180-DEG 190 ℃ fraction (2-3mmHg) was collected as a colorless, slightly viscous liquid, the yield was 86.6%, and the content of gas chromatography was 99.7%.
Example 4
The difference from the embodiment 1 is that:
196g (about 1.0mol) of C was charged at room temperature (about 25 ℃ C.)12-C14Adding long-chain mixed alkyl alcohol and 139g (1.5mol) of epichlorohydrin into a single-neck flask, and magnetically stirring until the materials are completely mixed to form a first raw material solution; adding 48g (1.2mol) of NaOH, 300ml of water and 9.67g (0.03mol) of tetrabutylammonium bromide into a single-neck round-bottom flask, and electromagnetically stirring until the materials are completely mixed to form a second raw material solution;
and (3) opening a heat exchange system of the microchannel reactor, setting the temperature of hot oil to be 60 ℃ to 60 +/-0.5 ℃ at a hot oil outlet of the microchannel reactor, starting two feeding pumps A and B, wherein the feeding pump A conveys a first raw material liquid, and the feeding pump B conveys a second raw material liquid. Wherein, the material conveying speed of the first raw material liquid and the second raw material liquid is 15ml/min, the retention time of the material is 1.6min, and the continuous feeding and the continuous discharging are carried out.
The reaction solution was received by a 1000ml four-necked round-bottomed flask, then the reaction solution was allowed to stand, the lower aqueous phase was separated, a small amount of water was added, washing was conducted once, the organic phase was distilled under reduced pressure, 180-DEG 190 ℃ fraction (2-3mmHg) was collected as a colorless, slightly viscous liquid, the yield was 87.4%, and the content of gas chromatography was 99.5%.
Example 5
The difference from the embodiment 1 is that:
196g (about 1.0mol) of C was charged at room temperature (about 25 ℃ C.)12-C14Adding long-chain mixed alkyl alcohol (commercially available) and 93g (1mol) of epichlorohydrin into a single-neck flask, and magnetically stirring until the materials are completely mixed to form a first raw material solution; adding 240g (6mol) of NaOH, 300ml of water and 110g (0.3mol) of ethyltriphenylphosphonium bromide into a single-neck round-bottom flask, and electromagnetically stirring until the materials are completely mixed to form a second raw material solution;
and (3) opening a heat exchange system of the microchannel reactor, setting the temperature of hot oil to be 60 ℃ to 60 +/-0.5 ℃ at a hot oil outlet of the microchannel reactor, starting two feeding pumps A and B, wherein the feeding pump A conveys a first raw material liquid, and the feeding pump B conveys a second raw material liquid. Wherein, the material conveying speed of the first raw material liquid and the second raw material liquid is 30ml/min, the retention time of the material is 1.6min, and the continuous feeding and the continuous discharging are carried out.
The reaction solution is received by a 1000ml four-mouth round-bottom flask, then the reaction solution is kept stand, the lower water phase is separated out, a small amount of water is added, the water is washed once, the organic phase is distilled under reduced pressure, 180-DEG C190 ℃ fraction (2-3mmHg) is collected, the product is colorless and slightly viscous liquid, the yield is 85.6 percent, and the content of gas chromatography is 99.2 percent.
Example 6
The difference from the embodiment 1 is that:
196g (about 1.0mol) of C was charged at room temperature (about 25 ℃ C.)12-C14Adding long-chain mixed alkyl alcohol (commercially available) and 111g (1.2mol) of epichlorohydrin into a single-neck flask, and magnetically stirring until the materials are completely mixed to form a first raw material solution; 120g (3mol) of NaOH, 300ml of water and 11g (0.03mol) of watermol) adding ethyltriphenyl phosphonium bromide into a single-mouth round-bottom flask, and electromagnetically stirring until the ethyl triphenyl phosphonium bromide and the single-mouth round-bottom flask are completely mixed to form a second raw material solution;
and (3) opening a heat exchange system of the microchannel reactor, setting the temperature of hot oil to be 60 ℃ to 60 +/-0.5 ℃ at a hot oil outlet of the microchannel reactor, starting two feeding pumps A and B, wherein the feeding pump A conveys a first raw material liquid, and the feeding pump B conveys a second raw material liquid. Wherein, the material conveying speed of the first raw material liquid and the second raw material liquid is 30ml/min, the retention time of the material is 1.6min, and the continuous feeding and the continuous discharging are carried out.
The reaction solution was received by a 1000ml four-necked round-bottomed flask, then the reaction solution was allowed to stand, the lower aqueous phase was separated, a small amount of water was added, washing was conducted once, the organic phase was distilled under reduced pressure, 180-DEG 190 ℃ fraction (2-3mmHg) was collected as a colorless, slightly viscous liquid, the yield was 83.5%, and the content of gas chromatography was 99.3%.
Comparative example 1
196g (about 1.0mol) of C was charged at room temperature (about 25 ℃ C.)12-C14Adding long-chain mixed alkyl alcohol, 9.67g (0.03mol) of tetrabutylammonium bromide, 48g (1.2mol) of NaOH and 300ml of water into a 1000ml four-neck flask, dropwise adding 139g (1.5mol) of epichlorohydrin for 2h, keeping the temperature at 40 ℃ for 1h after dropwise adding, then heating to 60 ℃, keeping the temperature for reaction for 3h, and stopping the reaction. After the reaction is finished, liquid is separated, the lower aqueous phase is separated, the organic phase is washed for 3 times by water until the organic phase is neutral, then reduced pressure distillation is carried out, 180-phase 190 ℃ fraction (2-3mmHg) is collected, the product is colorless and slightly viscous liquid, the yield is 67.4%, and the content of the gas chromatography is 99.4%.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of alkyl glycidyl ether is characterized in that alkyl alcohol and halogenated propylene oxide are subjected to the following continuous flow substitution reaction in a microchannel reactor to obtain the alkyl glycidyl ether;
the alkyl alcohol comprises one or more of compounds shown in a formula I, and n in the formula I is 12-14; the epoxy halogenated propane has a structure shown in a formula II, and X in the formula II is a halogen atom.
2. The method for preparing alkyl glycidyl ether according to claim 1, wherein the alkyl alcohol is a mixture of compounds in formula I in which n is 12-14, and the epihalohydrin is epichlorohydrin.
3. The process for preparing alkyl glycidyl ethers according to claim 1 or 2, characterized in that the continuous flow substitution 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, ethyltriphenylphosphonium bromide and ethyltriphenylphosphonium iodide;
preferably, the liquid alkali is selected from aqueous solutions of sodium hydroxide.
4. The process for the preparation of alkyl glycidyl ethers according to claim 3, characterized in that it comprises the following steps:
mixing the alkyl alcohol with the epihalohydrin to form a first feed solution;
mixing the catalyst with the liquid caustic to form a second feedstock;
and feeding the first raw material liquid and the second raw material liquid into the microchannel reactor to perform continuous flow substitution reaction to obtain the alkyl glycidyl ether.
5. The method of claim 4, 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 substitution product to obtain the alkyl glycidyl ether.
6. The method for preparing alkyl glycidyl ether according to claim 4, wherein the feeding rates of the first raw material and the second raw material during the continuous flow substitution reaction are respectively and independently selected from 10 to 30 ml/min; preferably, 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).
7. The method according to any one of claims 4 to 6, wherein the total retention time of the first feed solution and the second feed solution in the microchannel reactor is 1 to 5 min.
8. The method for producing an alkyl glycidyl ether according to any one of claims 4 to 6, wherein the molar ratio of the alkyl alcohol to the 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 the alkyl alcohol to the catalyst is 1 (0.03-0.3).
9. The method for preparing alkyl glycidyl ethers according to any of claims 1 to 6, characterized in that the temperature of the continuous flow substitution reaction is 50 to 70 ℃.
10. The method for producing an alkyl glycidyl ether according to claim 5, wherein the step of purifying the substitution product comprises:
standing and layering the substitution 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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| CN115947702A (en) * | 2022-12-12 | 2023-04-11 | 江苏扬农锦湖化工有限公司 | Preparation method of octyl glycidyl ether |
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| CN114213270A (en) * | 2021-12-17 | 2022-03-22 | 江苏阿尔法药业股份有限公司 | Method for synthesizing atorvastatin calcium intermediate by using continuous flow microchannel reactor |
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| 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 |
| CN115947702A (en) * | 2022-12-12 | 2023-04-11 | 江苏扬农锦湖化工有限公司 | Preparation method of octyl 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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