CN109721491B - Application and method of immobilized ionic liquid in catalytic synthesis of n-butyl carboxylate - Google Patents
Application and method of immobilized ionic liquid in catalytic synthesis of n-butyl carboxylate Download PDFInfo
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Abstract
The invention relates to the technical field of organic synthesis, and particularly discloses application and a method of immobilized ionic liquid in catalytic synthesis of n-butyl carboxylate, wherein a carrier in the immobilized ionic liquid is silica gel, and an ionic liquid is
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to application of immobilized ionic liquid in catalytic synthesis of n-butyl carboxylate and a method thereof.
Background
Esterification is one of the important reactions in organic synthesis, and has wide application in chemical products such as perfumes, plasticizers, solvents and the like. With the development of economy, higher requirements are put forward on the industrial production of ester products. The traditional esterification reaction using concentrated sulfuric acid as a strong acid catalyst has the problems of strong corrosivity, difficult treatment of waste liquid, more side reactions and the like. A plurality of heteropoly acids which are researched later are used as catalysts, and the problems of low catalytic efficiency, easy volatilization, difficult recovery and the like exist. And the traditional immobilized acid catalyst also has the problems of low selectivity, low catalytic activity, harsh reaction conditions and the like.
In recent years, the functionalized ionic liquid serving as a novel solvent and catalyst meets the requirement of green chemistry, is easy to recover, is widely applied to the fields of catalytic reaction, separation engineering, electrochemistry and the like, and receives more and more attention due to the unique catalytic performance. With the progress of research, researchers introduce carriers into the preparation of ionic liquid, and the ionic liquid is immobilized by utilizing the carriers such as silica gel, molecular sieves, mesoporous nano materials and the like, so that the ionic liquid is prevented from being mutually soluble with a solvent, a reactant or a product, the stability and the utilization rate of the ionic liquid are improved, and meanwhile, due to the physical and chemical action between the ionic liquid and the carriers, the catalytic performance can be further improved, and a new research field is developed.
However, ionic liquids mostly have higher selectivity for catalytic esterification reactions, and no clear guiding principle can be found for how to select ionic liquids for specific esterification reactions. The low-carbon carboxylic ester plays an important role in the field of chemical synthesis, and the finding of the immobilized ionic liquid suitable for catalyzing the carboxylic ester is of great significance.
Disclosure of Invention
In view of the technical current situation, the invention provides an application of immobilized ionic liquid in catalytic synthesis of lower carboxylic acid n-butyl ester, and provides a specific catalytic synthesis method.
In order to achieve the purpose, the invention adopts the following technical scheme:
the application of immobilized ionic liquid in catalytic synthesis of n-butyl carboxylate is characterized in that silica gel is used as a carrier in the immobilized ionic liquid, and the ionic liquid is
Wherein R is ethyl, butyl or octyl, and the carboxylic acid used in the carboxylic acid n-butyl ester is C1-C4 carboxylic acid.
The method for synthesizing the n-butyl carboxylate by utilizing the immobilized ionic liquid catalysis comprises the following steps: adding the immobilized ionic liquid, a water-carrying agent, carboxylic acid and n-butyl alcohol into a reactor, heating until reflux reaction is carried out for 0.5-6 h, separating water generated in the reaction process, recovering the immobilized ionic liquid catalyst after the reaction is finished, and separating reaction liquid to obtain a product, namely n-butyl carboxylate.
Preferably, the molar ratio of the carboxylic acid to the n-butanol is 1.1-1.2: 1.
Preferably, the loading amount of the ionic liquid in the immobilized ionic liquid is 7-54 wt%, and the loading amount refers to the percentage of the ionic liquid in the mass of the carrier silica gel.
Preferably, the dosage of the immobilized ionic liquid is 0.5-10% of the mass of the n-butyl alcohol.
Preferably, the ionic liquid is immobilized on the carrier silica gel by a sol-gel method.
Preferably, the method for immobilizing the ionic liquid on the carrier silica gel by adopting a sol-gel method comprises the following steps: dissolving the ionic liquid in absolute ethyl alcohol, adding the absolute ethyl alcohol into heated tetraethoxysilane, then dropwise adding concentrated hydrochloric acid and water, stopping heating after dropwise adding, standing to generate gel, aging and drying to obtain the immobilized ionic liquid.
Preferably, the water-carrying agent is cyclohexane, and the using amount of the water-carrying agent is 1-1.5 times of the volume of the n-butyl alcohol.
Preferably, the method for separating the n-butyl carboxylate from the reaction solution comprises the steps of firstly removing the water-carrying agent by rotary evaporation of the reaction solution, then washing the reaction solution by using a saturated sodium chloride solution and a saturated sodium carbonate solution to remove residual reactants, and drying the reaction solution to obtain the product, namely the n-butyl carboxylate.
The immobilized ionic liquid selected by the invention has the advantages of low price, simple preparation, environmental protection, higher selectivity for esterification reaction of C1-C4 carboxylic acid and n-butyl alcohol, less ionic liquid consumption and high catalytic efficiency.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Examples 1 to 12
The specific experimental procedure for examples 1-12 was:
respectively weighing carboxylic acid, n-butyl alcohol, immobilized ionic liquid and water-carrying agent cyclohexane, adding the carboxylic acid, n-butyl alcohol, immobilized ionic liquid and water-carrying agent cyclohexane into a three-neck flask with a reflux condenser, a water separator and magnetic stirring, heating to reflux for reaction, removing cyclohexane by rotary evaporation after the reaction is finished, washing with saturated sodium chloride solution and saturated sodium carbonate solution to remove residual reactants, drying with anhydrous magnesium sulfate to obtain a product n-butyl formate, and recovering and drying the immobilized ionic liquid for reuse.
Example 13
The effects of catalyzing the esterification reaction are shown in table 1, on the premise that the supported 1-methyl-3-ethylimidazole hydrogensulfate ionic liquid recovered in example 1, the supported 1-methyl-3-butylimidazole hydrogensulfate ionic liquid recovered in example 5, and the supported 1-methyl-3-octylimidazole hydrogensulfate ionic liquid recovered in example 9 were washed, dried at 80 ℃ and recycled, and other experimental conditions were the same as those of example 1, example 5, and example 9, respectively.
TABLE 1 Experimental study of the recycling of immobilized ionic liquids
As can be seen from the results in Table 1, the immobilized ionic liquid selected by the invention can be recycled for more than 5 times without regeneration in the esterification reaction.
Comparative examples 1 to 8
The reaction conditions of comparative examples 1 to 4 except the ionic liquid are the same as those of examples 1 to 4, and the reaction conditions of comparative examples 5 to 8 except the ionic liquid are the same as those of examples 5 to 8.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (3)
1. A method for synthesizing n-butyl carboxylate by catalysis of immobilized ionic liquid is characterized in that 0.4g of immobilized ionic liquid, 10mL of cyclohexane as a water-carrying agent, 0.12mol of butyric acid and 0.1mol of n-butyl alcohol are added into a reactor, the mixture is heated to reflux and reacted for 4 hours, water generated in the reaction process is separated, the immobilized ionic liquid catalyst is recovered after the reaction is finished, and the reaction solution is separated to obtain the product n-butyl carboxylate; the carrier in the immobilized ionic liquid is silica gel, and the ionic liquid is
Wherein R is ethyl; the loading amount of the ionic liquid in the immobilized ionic liquid is 20.7 wt%.
2. A method for synthesizing n-butyl carboxylate by catalysis of immobilized ionic liquid is characterized in that 2.4g of immobilized ionic liquid, 100mL of cyclohexane as a water-carrying agent, 1.1mol of acetic acid and 1mol of n-butyl alcohol are added into a reactor, the mixture is heated to reflux and reacted for 3.5 hours, water generated in the reaction process is separated, the immobilized ionic liquid catalyst is recovered after the reaction is finished, and the reaction liquid is separated to obtain the product n-butyl carboxylate; the carrier in the immobilized ionic liquid is silica gel, and the ionic liquid is
Wherein R is octyl; the loading amount of the ionic liquid in the immobilized ionic liquid is 7.8 wt%.
3. A method for synthesizing n-butyl carboxylate by catalysis of immobilized ionic liquid is characterized in that 0.5g of immobilized ionic liquid, 10mL of cyclohexane as a water-carrying agent, 0.12mol of butyric acid and 0.1mol of n-butyl alcohol are added into a reactor, the mixture is heated to reflux and reacted for 4 hours, water generated in the reaction process is separated, the immobilized ionic liquid catalyst is recovered after the reaction is finished, and the reaction solution is separated to obtain the product n-butyl carboxylate; the carrier in the immobilized ionic liquid is silica gel, and the ionic liquid is
Wherein R is octyl; the loading amount of the ionic liquid in the immobilized ionic liquid is 40.1 wt%.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106905150A (en) * | 2017-02-10 | 2017-06-30 | 长春工业大学 | A kind of synthetic method of n-butyl acetate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106905150A (en) * | 2017-02-10 | 2017-06-30 | 长春工业大学 | A kind of synthetic method of n-butyl acetate |
Non-Patent Citations (2)
| Title |
|---|
| Continuous Transesterification with Acidic Ionic Liquids as Homogeneous Catalysts;Kuschnerow, JC.et al;《CHEMICAL ENGINEERING & TECHNOLOGY》;20131031;第36卷(第10期);第1643-1650页 * |
| 固载化酸性离子液体催化酯化反应研究;梁丽亚;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20131215;B016-5 * |
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