CN107056592B - Post-treatment method of 2-propoxyl chloroethane crude product - Google Patents
Post-treatment method of 2-propoxyl chloroethane crude product Download PDFInfo
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- CN107056592B CN107056592B CN201710055926.4A CN201710055926A CN107056592B CN 107056592 B CN107056592 B CN 107056592B CN 201710055926 A CN201710055926 A CN 201710055926A CN 107056592 B CN107056592 B CN 107056592B
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
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Abstract
The invention relates to 2-propoxyl chloroethane, in particular to a post-treatment method of a 2-propoxyl chloroethane crude product. The post-treatment method of the 2-propoxychloroethane crude product comprises the following steps: heating and gasifying the formic acid solution, and introducing the gasified gas into anhydrous copper sulfate or boric anhydride solution for drying; introducing the dried formic acid gas into the crude product of 2-propoxyl chloroethane for reaction; after the reaction is finished, the reaction solution is vacuumized to obtain a pure 2-propoxyl chloroethane product. The invention uses formic acid to react with thionyl chloride in the crude product of 2-propoxyl chloroethane to generate sulfur dioxide, hydrogen chloride and carbon monoxide, and no other impurities are generated, thereby obtaining the pure product of 2-propoxyl chloroethane, the product appearance is clear and transparent, the purity reaches more than 99.5 percent, and the yield is more than 98 percent. Compared with the traditional process, the method has the advantages of no wastewater generation, no distillation, simple post-treatment process, high purity and yield, and suitability for industrial production.
Description
Technical Field
The invention relates to 2-propoxyl chloroethane, in particular to a post-treatment method of a 2-propoxyl chloroethane crude product.
Background
The 2-propoxychloroethane is one of important raw materials for preparing herbicide pretilachlor, is high-efficiency and low-toxicity, is a professional selective bud-stage herbicide for an early broad-spectrum rice field, and is widely applied to the field of rice planting. With the current situation in the aspects of environmental protection and safety and the rapid development trend of the pesticide industry, the demand of 2-propoxyl chloroethane is continuously increased, and higher requirements on the quality and the process environmental protection are also provided.
The traditional preparation process of 2-propoxyl chloroethane mainly adopts excessive thionyl chloride to carry out chlorine substitution reaction with the excessive thionyl chloride to obtain a crude product of the 2-propoxyl chloroethane, and the crude product is subjected to post-treatment to obtain a pure product. The post-treatment of the crude product is generally to neutralize the crude product with alkali liquor, extract the crude product with water for many times, and then distill the crude product to obtain a pure 2-propoxychloroethane product, wherein the yield can reach over 90 percent. Although the yield is high, the product quality is unstable due to excessive thionyl chloride. And the post-treatment process is complicated and high in cost, and particularly, a large amount of waste water is generated after multiple times of neutralization and extraction, so that the environmental pollution is caused.
Therefore, on the premise of ensuring the product yield, the development of an efficient, safe and environment-friendly post-treatment method for the 2-propoxychloroethane crude product has important practical significance.
Disclosure of Invention
The invention aims to provide a post-treatment method of a 2-propoxyl chloroethane crude product, which has the advantages of simple process, safe operation, no impurity and no wastewater generation, and obviously improves the product purity and yield.
The post-treatment method of the 2-propoxychloroethane crude product comprises the following steps:
(1) heating and gasifying the formic acid aqueous solution, and drying the gasified gas;
(2) introducing the dried formic acid gas into the crude product of 2-propoxyl chloroethane for reaction;
(3) after the reaction is finished, the reaction solution is vacuumized to obtain a pure 2-propoxyl chloroethane product.
Wherein:
in the step (1), the mass concentration of the formic acid aqueous solution is 70-85%.
In the step (1), the gasification temperature of the formic acid is 115-130 ℃.
In the step (1), the gasified gas is introduced into anhydrous copper sulfate or boric anhydride for drying.
In the step (2), the 2-propoxychloroethane crude product is prepared by using Lewis acid as a catalyst and reacting ethylene glycol mono-n-propyl ether and thionyl chloride in a mass ratio of 1: 1.05-1.15. The Lewis acid catalyst is one or more of aluminum chloride, ferric chloride, boron trifluoride, niobium pentachloride or zinc chloride.
In the step (2), the reaction is carried out for 2 to 7 hours at a temperature of 80 to 100 ℃.
In the step (2), the content of the thionyl chloride in the crude 2-propoxychloroethane is measured by a chemical analysis method, and the mass ratio of the introduced dried formic acid gas to the thionyl chloride in the crude 2-propoxychloroethane is 1:1.
In the step (3), the vacuumizing time is 2-4 hours, and the vacuum degree is 0.01-0.05 MPa.
In the step (3), the mass content of the obtained 2-propoxyl chloroethane pure product is more than 99.5 percent, and the yield is more than 98 percent.
The invention has the following beneficial effects:
the invention uses formic acid to react with thionyl chloride in the crude product of 2-propoxyl chloroethane to generate sulfur dioxide, hydrogen chloride and carbon monoxide, and no other impurities are generated, thereby obtaining the pure product of 2-propoxyl chloroethane, the product appearance is clear and transparent, the purity reaches more than 99.5 percent, and the total yield is more than 98 percent. Compared with the traditional process, the method has the advantages of no wastewater generation, no distillation, simple post-treatment process, high purity and yield, and suitability for industrial production.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
(1) 0.1g of aluminum chloride and 0.1g of zinc chloride are used as catalysts, 200g of ethylene glycol mono-n-propyl ether and 262g of thionyl chloride are reacted to obtain 265g of crude 2-propoxychloroethane; through chemical analysis, the mass content of the thionyl chloride in the crude product is 12.6%;
(2) heating 85 wt% formic acid water solution at 130 deg.C for gasification, introducing gasified gas into anhydrous copper sulfate for drying, introducing dried formic acid gas into 2-propoxychloroethane crude product, and reacting at 100 deg.C for 2 hr; the mass of the dried formic acid gas is 14.17 g;
(3) after the reaction is finished, the reaction solution is vacuumized for 3 hours under the vacuum degree of 0.01MPa to obtain 231g of 2-propoxyl chloroethane pure product, the chromatographic content of the product is 99.53 percent through detection, and the total yield reaches 98.1 percent.
Example 2
(1) 0.25g of ferric chloride is used as a catalyst, 200g of ethylene glycol mono-n-propyl ether and 251g of thionyl chloride are reacted to obtain 254g of crude 2-propoxychloroethane; through chemical analysis, the mass content of the thionyl chloride in the crude product is 8.7%;
(2) heating 70 wt% formic acid water solution at 115 ℃ for gasification, introducing the gasified gas into boric anhydride for drying, introducing the dried formic acid gas into a 2-propoxychloroethane crude product, and reacting at 80 ℃ for 7 hours; the mass of the dried formic acid gas is 9.28 g;
(3) after the reaction is finished, the reaction solution is vacuumized for 2.5 hours under the vacuum degree of 0.02MPa to obtain 232g of 2-propoxyl chloroethane pure product, the chromatographic content of the product is 99.67 percent through detection, and the total yield reaches 98.5 percent.
Example 3
(1) 0.2g of zinc chloride is used as a catalyst, 200g of ethylene glycol mono-n-propyl ether and 240g of thionyl chloride are reacted to obtain 244g of 2-propoxychloroethane crude product; through chemical analysis, the mass content of the thionyl chloride in the crude product is 4.7%;
(2) heating 75 wt% formic acid water solution at 120 deg.C for gasification, introducing gasified gas into anhydrous copper sulfate for drying, introducing dried formic acid gas into 2-propoxychloroethane crude product, and reacting at 90 deg.C for 4 hr; the mass of the dried formic acid gas is 4.85 g;
(3) after the reaction is finished, the reaction solution is vacuumized for 2 hours under the vacuum degree of 0.05MPa to obtain 233g of 2-propoxyl chloroethane pure product, and the chromatographic content of the product is 99.72% through detection, and the total yield reaches 98.9%.
Example 4
(1) Taking 0.15g of niobium pentachloride as a catalyst, reacting 200g of ethylene glycol mono-n-propyl ether and 257g of thionyl chloride to obtain 261g of crude 2-propoxyl chloroethane; through chemical analysis, the mass content of the thionyl chloride in the crude product is 10.9%;
(2) heating 80 wt% formic acid water solution at 127 deg.C for gasification, introducing gasified gas into anhydrous copper sulfate for drying, introducing dried formic acid gas into 2-propoxychloroethane crude product, and reacting at 85 deg.C for 5 hr; the mass of the dried formic acid gas is 12 g;
(3) after the reaction is finished, the reaction solution is vacuumized for 4 hours under the vacuum degree of 0.04MPa to obtain 232.5g of 2-propoxyl chloroethane pure product, the chromatographic content of the product is 99.72% through detection, and the total yield reaches 98.7%.
Comparative example 1
(1) 0.1g of aluminum chloride and 0.1g of zinc chloride are used as catalysts, 200g of ethylene glycol mono-n-propyl ether and 262g of thionyl chloride are reacted to obtain 265g of crude 2-propoxychloroethane; through chemical analysis, the mass content of the thionyl chloride in the crude product is 12.6%;
(2) adding 30% liquid caustic soda solution to the solution to neutralize until pH value is neutral, adding 200ml water for extraction, and continuously extracting the upper layer organic liquid for 3 times;
(3) and (3) putting the solution into a round-bottom flask, heating to 135-145 ℃, distilling at normal pressure, controlling the rectification speed to obtain 212g of 2-propoxychloroethane pure product, and detecting that the chromatographic content of the product is 96.7% and the total yield reaches 90%.
Comparative example 2
(1) 0.25g of ferric chloride is used as a catalyst, 200g of ethylene glycol mono-n-propyl ether and 251g of thionyl chloride are reacted to obtain 254g of crude 2-propoxychloroethane; through chemical analysis, the mass content of the thionyl chloride in the crude product is 8.7%;
(2) adding 30% liquid caustic soda solution to the solution to neutralize until pH value is neutral, adding 200ml water for extraction, and continuously extracting the upper layer organic liquid for 3 times;
(3) and (3) putting the solution into a round-bottom flask, heating to 135-145 ℃, distilling at normal pressure, controlling the rectification speed to obtain 214.2g of 2-propoxychloroethane pure product, and detecting that the chromatographic content of the product is 97.2% and the total yield reaches 91%.
Comparative example 3
(1) 0.2g of zinc chloride is used as a catalyst, 200g of ethylene glycol mono-n-propyl ether and 240g of thionyl chloride are reacted to obtain 244g of 2-propoxychloroethane crude product; through chemical analysis, the mass content of the thionyl chloride in the crude product is 4.7%;
(2) adding 30% liquid caustic soda solution to the solution to neutralize until pH value is neutral, adding 200ml water for extraction, and continuously extracting the upper layer organic liquid for 3 times;
(3) and (3) putting the solution into a round-bottom flask, heating to 135-145 ℃, distilling at normal pressure, controlling the rectification speed to obtain 213.5g of 2-propoxychloroethane pure product, and detecting that the chromatographic content of the product is 96.9% and the total yield reaches 90.7%.
Claims (6)
1. The post-treatment method of the 2-propoxychloroethane crude product is characterized by comprising the following steps:
(1) heating and gasifying the formic acid aqueous solution, and drying the gasified gas;
(2) introducing the dried formic acid gas into the crude product of 2-propoxyl chloroethane for reaction;
(3) after the reaction is finished, vacuumizing the reaction liquid to obtain a pure 2-propoxyl chloroethane product;
in the step (2), the 2-propoxychloroethane crude product is prepared by taking Lewis acid as a catalyst and reacting ethylene glycol mono-n-propyl ether with thionyl chloride in a mass ratio of 1: 1.05-1.15;
in the step (2), the mass ratio of the dried formic acid gas to the thionyl chloride in the crude product of 2-propoxychloroethane is 1: 1;
in the step (2), reacting for 2-7 hours at 80-100 ℃;
in the step (3), the vacuumizing time is 2-4 hours, and the vacuum degree is 0.01-0.05 MPa.
2. The method of claim 1, wherein the method comprises the following steps: in the step (1), the mass concentration of the formic acid aqueous solution is 70-85%.
3. The method of post-treatment of crude 2-propoxychloroethane as claimed in claim 1 or 2, wherein: in the step (1), the gasification temperature of the formic acid is 115-130 ℃.
4. The method of post-treatment of crude 2-propoxychloroethane as claimed in claim 1 or 2, wherein: in the step (1), the gasified gas is introduced into anhydrous copper sulfate or boric anhydride for drying.
5. The method of claim 1, wherein the method comprises the following steps: the Lewis acid catalyst is one or more of aluminum chloride, ferric chloride, boron trifluoride, niobium pentachloride or zinc chloride.
6. The method of claim 1, wherein the method comprises the following steps: in the step (3), the mass content of the obtained 2-propoxyl chloroethane pure product is more than 99.5 percent, and the yield is more than 98 percent.
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| CN105348052A (en) * | 2015-12-14 | 2016-02-24 | 山东凯盛新材料有限公司 | Synthesis process of 2-propoxy-chloroethane |
| WO2016202894A1 (en) * | 2015-06-17 | 2016-12-22 | Universitaet Des Saarlandes | Method of converting alcohol to halide |
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| WO2016202894A1 (en) * | 2015-06-17 | 2016-12-22 | Universitaet Des Saarlandes | Method of converting alcohol to halide |
| CN105348052A (en) * | 2015-12-14 | 2016-02-24 | 山东凯盛新材料有限公司 | Synthesis process of 2-propoxy-chloroethane |
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