CN113651688B

CN113651688B - Preparation method of fatty acyl chloride

Info

Publication number: CN113651688B
Application number: CN202110921844.XA
Authority: CN
Inventors: 张静; 蔺海政; 鲍元野; 桂振友; 张德旸
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2021-08-12
Filing date: 2021-08-12
Publication date: 2022-08-05
Anticipated expiration: 2041-08-12
Also published as: CN113651688A

Abstract

The invention provides a method for preparing fatty acyl chloride, fatty acid and solid phosgene are reacted under the catalysis of a catalyst to prepare the fatty acyl chloride, and the solid phosgene is adopted to replace virulent phosgene.

Description

Preparation method of fatty acyl chloride

Technical Field

The invention relates to the field of acyl chlorination reaction, and particularly relates to a preparation method of fatty acyl chloride.

Background

Acyl chloride is an important intermediate. At present, the acyl chlorination method mainly comprises a phosphorus trichloride method, a sulfoxide chloride method, a phosphorus pentachloride method, a phosgene method, a solid phosgene (triphosgene) method and the like.

The phosphorous acid as a by-product and the product are difficult to completely separate out in the phosphorus trichloride method, and the obtained product needs to be rectified, so that the yield of the product is low, the method is mainly suitable for preparing the acyl chloride with low boiling point, and the phosphorous acid generated in the reaction is difficult to volatilize, so that the acyl chloride can be conveniently distilled out. The phosphorus pentachloride method needs solid feeding and is easy to absorb moisture. The thionyl chloride method for preparing acyl chloride has mild reaction conditions, and can react at room temperature or by slight heating, the products except acyl chloride are all gases, and the products can be applied without purification, and have good purity and high yield, but if the boiling point of the generated acyl chloride is close to that of thionyl chloride, the products are not easy to separate from the thionyl chloride; in addition, the method has the disadvantages of large consumption of thionyl chloride, usually more than twice of the molar weight of carboxylic acid, high production cost and serious corrosion to equipment. At present, the phosgene acyl chlorination method is ideal, the product content is high, the yield is high, however, phosgene is a highly toxic gas and has great danger in the using, transporting and storing processes, and the source of phosgene is limited.

Solid phosgene has a high melting point, low volatility and low toxicity, and is decomposed only in a small amount even at the boiling point, and is industrially treated only as a general toxic substance, and therefore, is often used as a substitute for phosgene. Moreover, the conditions required for the synthesis and the participation of the solid phosgene in the chemical reaction are very mild, and the method has the advantages of strong selectivity, high yield, safe and convenient use, and easy transportation and storage. The compound can completely replace phosgene or diphosgene to participate in the synthesis of related chemicals in the aspects of medicines, pesticides, organic chemical industry, high polymer materials and the like, and is increasingly widely applied. However, solid phosgene is rarely used as an acyl chlorinating agent in chemical reactions and chemical production at home and abroad so far, and the main reason is that the catalyst is difficult to select.

In the traditional preparation process of acyl chloride by using solid phosgene as an acyl chlorinating agent, N-Dimethylformamide (DMF) is usually selected as a catalyst for reaction, and the flash point of the catalyst is 58 ℃, and the catalyst belongs to combustible liquid. The explosion limit is 2.2-15.2%, and the explosion risk exists. The fatty acid chloride is decomposed into formic acid and dimethylamine salt under the action of acid, and is decomposed into formate and dimethylamine under the action of alkali, and in a system with acid, alkali and water, the fatty acid chloride is unstable in chemical property, belongs to a low-toxicity substance, is used for preparing a basic raw material fatty acid chloride for producing a surfactant and a humectant in the personal care product industry, and has certain potential safety hazard.

Disclosure of Invention

The invention aims to provide a preparation method of fatty acyl chloride, which takes solid phosgene as an acyl chlorination reagent, adopts a new catalyst, has high catalyst activity, high product yield and mild reaction conditions, is used as a cosmetic additive, has a sun-screening effect and simplifies the post-treatment process.

In order to solve the problems, the invention provides a preparation method of fatty acyl chloride, which comprises the step of reacting fatty acid solid phosgene under the catalysis of a catalyst in an inert gas environment to prepare the fatty acyl chloride.

Preferably, the catalyst is zinc oxide.

In some preferred embodiments of the present invention, the preparation method of the present invention comprises the steps of:

(1) the inert gas replaces the air in the reaction kettle, the product color may be deepened due to the existence of oxygen, and spontaneous combustion can be caused by high-temperature reaction;

(2) adding fatty acid and zinc oxide into a reaction kettle, heating and preheating, and adding solid phosgene;

(3) heating to the reaction temperature, and reacting for a period of time;

in the step (2) of the present invention, the preheating temperature is 130-; a pressure of 0.1 to 1MPa, preferably 0.2 to 0.9MPa, more preferably 0.3 to 0.5MPa in terms of gauge pressure; the residence time is 20-50min, preferably 25-48min, more preferably 30-45 min.

Preferably, the fatty acid is a linear saturated fatty acid of C8, C10, C12, C14, C16, C18, preferably a linear saturated fatty acid of C10, C12, C14, more preferably lauric acid.

The molar ratio of the addition amount of the fatty acid to the solid phosgene is 2:1-4:1, preferably 2.5:1-3.5:1, more preferably 2.8:1-3.2: 1;

the mass ratio of the catalyst zinc oxide to the fatty acid is 0.003-0.028: 1, preferably 0.008 to 0.026: 1, more preferably 0.009-0.022: 1.

in the invention, the reaction temperature is 170-200 ℃, preferably 175-195 ℃, and more preferably 180-190 ℃; the reaction time is 20-120min, preferably 30-100min, and more preferably 40-90 min.

In the present invention, the fatty acid and/or the solid phosgene needs to be dehydrated, and the dehydration may be performed before the raw material is added, or may be performed after the solid phosgene is added in the step (2).

In the invention, after the reaction is finished, the reaction liquid is transferred into a melting buffer kettle, the operation temperature of the kettle is 180-200 ℃, and the continuous granulation and packaging are carried out by buffering in the nitrogen atmosphere.

The invention has the positive effects that:

(1) the fatty acid is adopted as the raw material, so that the method is safe and reliable and has no toxic or side effect;

(2) the zinc oxide catalyst has good catalytic activity in the reaction, and the solid catalyst has stable chemical property, can be used as a physical sun-screening agent to be added into a product, does not need to be purified, and has simple post-treatment process and low production cost.

(3) The reaction operation condition is mild, and the industrial production is easy to realize.

(4) The fatty acyl chloride of the invention can be used for synthesizing a surfactant and can also be used as a basic raw material for producing a humectant.

Detailed Description

The following examples are not intended to limit the scope of the present invention, and modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is defined in the appended claims.

Catalyst zinc oxide was purchased from MACKLIN; 98 wt% lauric acid (C12), 99 wt% n-octanoic acid (C8), 99 wt% n-decanoic acid (C10), 99 wt% phosgene solid was purchased from Shanghai Michelin Biotech, Inc.; 99 wt% palmitic acid (C16), 99 wt% myristic acid (C14) from Merck Supelco, and 99.9 wt% N, N-Dimethylformamide (DMF) from aladdin.

The yield of the lauroyl chloride is obtained by analyzing and calculating liquid chromatogram which is 1200 series of Agilent company and is provided with a C18 liquid chromatogram column, the column temperature is set to be 40 ℃, acetonitrile and 0.05mol/L NaH2PO4 solution are used as mobile phases, the flow rate is 1.0mL/min, the detection is carried out at the wavelength of 360nm by an ultraviolet detector, and the quantification is carried out by an external standard method. Before sample introduction, a sample is diluted properly by ultrapure water, added with excessive dinitrofluorobenzene solution for full derivatization, and then subjected to sample introduction analysis.

Example 1

Replacing air in the kettle with nitrogen, adding 870g of lauric acid (C12 fatty acid) and 8.526g of zinc oxide into a reaction kettle with a stirrer, heating to 160 ℃, adding 425g of solid phosgene under the condition of 0.5MPa, removing water in raw materials into a wastewater tank, standing for 30min, heating to 190 ℃ after water brought by the raw materials is removed, standing for 50min, finishing the reaction, transferring reaction liquid into a melting buffer kettle, performing buffer under the nitrogen atmosphere at the operation temperature of 190 ℃, performing continuous granulation and packaging, and obtaining the reaction yield of 87%.

Data obtained from nuclear magnetic spectrum of lauroyl chloride: chemical shift 0.7-1 multiplet 3H; chemical shift 1.2-1.6 multiple peak 18H; chemical shifts 2.7-2.9 multiple peak 2H.

Example 2

Replacing air in the kettle with nitrogen, adding 620g of n-octanoic acid (C8 fatty acid) and 2g of zinc oxide into the reaction kettle, heating to 160 ℃, adding 425g of solid phosgene under the condition of 0.5MPa, removing water in the raw materials into a wastewater tank, standing for 30min, heating to 190 ℃ after water brought by the raw materials is completely removed, standing for 50min, finishing the reaction, transferring the reaction liquid into a melting buffer kettle, performing buffer under the nitrogen atmosphere, performing continuous granulation and packaging, wherein the reaction yield is 63%.

Example 3

Replacing air in the kettle with nitrogen, adding 690g of n-decanoic acid (C10 fatty acid) and 6.9g of zinc oxide into the reaction kettle, heating to 130 ℃, adding 396g of solid phosgene under the condition of 0.1MPa, removing water in the raw materials into a wastewater tank, standing for 50min, heating to 170 ℃ after water brought by the raw materials is removed, standing for 40min, finishing the reaction, transferring the reaction liquid into a melting buffer kettle, performing buffer granulation and packaging under the nitrogen atmosphere at the kettle operation temperature of 200 ℃, and obtaining the reaction yield of 67%.

Example 4

After the air in the kettle is replaced by nitrogen, 505g of myristic acid (C14 fatty acid) and 5g of zinc oxide are added into the reaction kettle, the temperature is raised to 160 ℃, 216.5g of solid phosgene is added under the condition of 0.4MPa, the water in the raw materials is removed to a waste water tank, the retention time is 50min, after the water brought by the raw materials is completely removed, the temperature is raised to 170 ℃, the reaction is stopped for 40min, the reaction liquid is transferred into a melting buffer kettle, the operation temperature of the kettle is 200 ℃, the reaction liquid is buffered under the nitrogen atmosphere for continuous granulation and packaging, and the reaction yield is 75%.

Example 5

The air in the kettle is replaced by nitrogen, 560g of palmitic acid (C16) and 6g of zinc oxide are added into the reaction kettle, the temperature is raised to 160 ℃, 229g of solid phosgene is added under the condition of 0.4MPa, the water in the raw materials is removed to a wastewater tank, the retention time is 50min, after the water brought by the raw materials is completely removed, the temperature is raised to 170 ℃, the reaction liquid is retained for 40min, the reaction is finished, the reaction liquid is transferred into a melting buffer kettle, the operation temperature of the kettle is 200 ℃, the continuous granulation and packaging are carried out by buffering in the nitrogen atmosphere, and the reaction yield is 70%.

Example 6

Replacing air in the kettle with nitrogen, adding 705g of lauric acid (C12 fatty acid) and 14g of zinc oxide into the reaction kettle, heating to 140 ℃, adding 413g of solid phosgene under the condition of 0.2MPa, removing water in the raw materials into a wastewater tank, standing for 40min, heating to 185 ℃ after water brought by the raw materials is completely removed, standing for 70min, finishing the reaction, transferring the reaction liquid into a melting buffer kettle, performing buffer under the nitrogen atmosphere at the operation temperature of 200 ℃, performing continuous granulation and packaging, and obtaining the reaction yield of 80%.

Comparative example 1

Replacing air in the kettle with nitrogen, adding 655g of lauric acid (C12 fatty acid) and 13g N, N-Dimethylformamide (DMF) into the reaction kettle, heating to 160 ℃, adding 317g of solid phosgene under the condition of 0.4MPa, removing water in raw materials into a wastewater tank, standing for 40min, heating to 185 ℃ after water brought by the raw materials is completely removed, standing for 70min, finishing the reaction, transferring reaction liquid into a melting buffer kettle, performing buffer under the nitrogen atmosphere, performing continuous granulation and packaging, and ensuring that the reaction yield is 59%.

Claims

1. A method for preparing fatty acyl chloride is characterized in that fatty acid and solid phosgene are reacted under the catalysis of a catalyst in an inert gas environment to prepare the fatty acyl chloride;

the catalyst is zinc oxide.

2. The method of claim 1, comprising the steps of:

(1) replacing air in the reaction kettle with inert gas;

(3) heating to reaction temperature, and reacting for a period of time.

3. The production method as claimed in claim 2, wherein in the step (2), the preheating temperature is 130-180 ℃, the pressure is 0.1-1MPa in gauge pressure, and the residence time is 20-50 min.

4. The production process according to claim 3, wherein in the step (2), the preheating temperature is 140 ℃ and 170 ℃, the pressure is 0.2 to 0.9MPa in gauge pressure, and the residence time is 25 to 48 min.

5. The method as claimed in claim 4, wherein the preheating temperature in step (2) is 150 ℃ to 160 ℃; the pressure is 0.3-0.5MPa according to gauge pressure; the retention time is 30-45 min.

6. The method according to claim 1 or 2, wherein the fatty acid is a linear saturated fatty acid of C8, C10, C12, C14, C16, C18.

7. The method according to claim 6, wherein the fatty acid is a linear saturated fatty acid of C10, C12, C14.

8. The production method according to claim 7, wherein the fatty acid is lauric acid.

9. The method according to claim 1 or 2, wherein the molar ratio of the fatty acid to the amount of phosgene solid added is 2:1-4: 1.

10. The method of claim 9, wherein the molar ratio of the fatty acid to the amount of the phosgene solid is 2.5:1-3.5: 1.

11. The method according to claim 10, wherein the molar ratio of the fatty acid to the amount of phosgene solid added is 2.8:1-3.2: 1.

12. The production method according to claim 1 or 2, wherein the mass ratio of the zinc oxide to the fatty acid is from 0.003 to 0.028: 1.

13. the preparation method according to claim 12, wherein the mass ratio of the zinc oxide to the fatty acid is 0.008 to 0.026: 1.

14. the method according to claim 13, wherein the mass ratio of the zinc oxide to the fatty acid is 0.009-0.022: 1.

15. the preparation method as claimed in claim 1 or 2, wherein the reaction temperature is 170-200 ℃ and the reaction time is 20-120 min.

16. The method as claimed in claim 15, wherein the reaction temperature is 175-195 ℃ and the reaction time is 30-100 min.

17. The method as claimed in claim 16, wherein the reaction temperature is 180-190 ℃; the reaction time is 40-90 min.

18. The production method according to claim 1 or 2, wherein the fatty acid and/or the solid phosgene is subjected to dehydration treatment before the reaction, and the dehydration treatment is performed before the addition of the raw material or after the addition of the solid phosgene in the step (2).

19. The preparation method as claimed in claim 1 or 2, wherein the reaction is completed, and the reaction solution is transferred to a melting buffer kettle, wherein the operation temperature of the kettle is 180 ℃ and 200 ℃, and the continuous granulation and packaging are carried out by buffering in a nitrogen atmosphere.