阅读说明：本技术 一种环氧氟丙烷的制备方法 (Preparation method of epoxyfluoropropane ) 是由 赵恒军 陈朝阳 丛鑫鑫 张伟 郑爱伟 于 2021-10-25 设计创作，主要内容包括：本发明公开一种环氧氟丙烷的制备方法,包括步骤：(1)氯化：以甘油为起始原料,羧酸为催化剂,50～150℃连续通入氯化氢气体,至反应完毕,停止通氯化氢,后处理,得产物1,3-二氯-2-丙醇；(2)氟氯交换：将得到的上述产物1,3-二氯-2-丙醇,加入丙酰胺,同时加入无机氟化盐,升温至150～250℃,反应1～5h,停止反应,分离得到1,3-二氟-2-丙醇；(3)Williamson环化：将1,3-二氟-2-丙醇加入反应釜中,加入强碱,分散溶剂,-20～50℃反应1～8h,反应完毕,过滤,精馏,得产物环氧氟丙烷。本发明原料廉价易得、反应过程温和可控,绿色经济,是一种适宜于工业化的制备方法。(The invention discloses a preparation method of epoxy fluoropropane, which comprises the following steps: (1) chlorination: taking glycerol as a starting material and carboxylic acid as a catalyst, continuously introducing hydrogen chloride gas at 50-150 ℃, stopping introducing the hydrogen chloride when the reaction is finished, and performing post-treatment to obtain a product 1, 3-dichloro-2-propanol; (2) fluorine-chlorine exchange: adding propionamide and inorganic fluoride salt into the obtained product 1, 3-dichloro-2-propanol, heating to 150-250 ℃, reacting for 1-5 hours, stopping the reaction, and separating to obtain 1, 3-difluoro-2-propanol; (3) williamson cyclization: adding 1, 3-difluoro-2-propanol into a reaction kettle, adding strong base and a dispersing solvent, reacting for 1-8 h at-20-50 ℃, filtering after the reaction is finished, and rectifying to obtain the product of the epoxyfluoropropane. The preparation method has the advantages of cheap and easily-obtained raw materials, mild and controllable reaction process, greenness and economy, and is a preparation method suitable for industrialization.)

1. A preparation method of epoxy fluoropropane comprises the following steps:

(1) chlorination: taking glycerol as a starting material and carboxylic acid as a catalyst, continuously introducing hydrogen chloride gas at 50-150 ℃, stopping introducing the hydrogen chloride when the reaction is finished, and performing post-treatment to obtain a product 1, 3-dichloro-2-propanol;

(2) fluorine-chlorine exchange: adding propionamide and inorganic fluoride salt into the obtained product 1, 3-dichloro-2-propanol, heating to 150-250 ℃, reacting for 1-5 hours, stopping the reaction, and separating to obtain 1, 3-difluoro-2-propanol;

(3) williamson cyclization: adding 1, 3-difluoro-2-propanol into a reaction kettle, adding strong base and a dispersing solvent, reacting for 1-8 h at-20-50 ℃, filtering after the reaction is finished, and rectifying to obtain the product of the epoxyfluoropropane.

The reaction chemical equation is as follows:

2. the method of claim 1, wherein the carboxylic acid catalyst is one of acetic acid, adipic acid, 3-chloropropionic acid, and malonic acid.

3. The method for producing an epifluoropropane as claimed in claim 2, wherein said carboxylic acid catalyst is added in an amount of 2 to 15% by mass based on the mass of glycerin.

4. The method according to claim 1, wherein the inorganic fluorine salt MF comprises one or more of sodium fluoride, potassium fluoride, ammonium fluoride, magnesium fluoride, lead fluoride, selenium hexafluoride, mercury fluoride, or lithium fluoride.

5. The method for producing an epifluoropropane as claimed in claim 4, wherein said inorganic fluorine salt: the mol ratio of 1, 3-dichloro-2-propanol is 5-1: 1.

6. the method of claim 1, wherein the strong base in the Williamson cyclization comprises one or more of an inorganic strong base such as sodium hydroxide, calcium hydroxide, potassium hydroxide, lithium hydroxide or barium hydroxide, and an organic strong base or a catalyst supporting a strong base.

7. The method of claim 6, wherein the strong base: the molar ratio of the 1, 3-difluoro-2-propanol is 10-1.5: 1.

8. The method for preparing epifluoropropane as claimed in claim 7, wherein the Williamson cyclization reaction temperature is-5 to 20 ℃ and the reaction time is 2 to 5 hours.

9. The method of producing an epifluoropropane as claimed in claim 1, wherein said dispersion solvent is one or more of petroleum ether, toluene, cyclohexane and trifluorotoluene.

Technical Field

The invention relates to the field of chemical industry, in particular to a preparation method of epoxy fluoropropane.

Background

Fluorine is the element with the strongest electronegativity among all elements discovered so far, has the atomic radius similar to that of a hydrogen atom, has strong biological activity and pseudo effect, is widely applied to the development and the development of novel medicines, and more than 40 percent of the novel medicines developed at present are fluorine-containing varieties. In addition, because the C-F bond constructed by the fluorine-containing compound and carbon atoms has super stability, the fluorine-containing compound has excellent physicochemical characteristics, is widely applied to the fields of dyes, refrigerants, new materials and the like, and is a strategic key new direction of chemical development in China. By means of an exemplary approach, the characteristic of fluorine atoms is utilized, and the fluorine atoms are used for replacing Cl or H in a known compound, so that the method is an effective method for developing a new material and is a shortcut for developing the new material. Compared with the original material, the newly developed material has the excellent characteristics of better corrosion resistance, thermal stability, low temperature resistance, low toxicity and the like, so that the application of the newly developed material in the related field is safer and more environment-friendly, and larger social benefits are generated.

Epichlorohydrin is an important organic chemical raw material and fine chemical products, can be used for epoxy resin, chlorohydrin rubber, adhesive, cation exchange resin and the like, and has wide application. In 2020, the global epichlorohydrin production capacity is about 300 ten thousand t, wherein china, usa, germany, russia and japan are the most important production countries and account for about 88% of the global production capacity, and wherein china is the largest production capacity country and accounts for about 50% of the total production capacity. The total global consumption is about 220 million, with asia, western europe and north america being the major consumer areas, accounting for 60%, 28% and 18% of the total consumption, respectively. With the slowing of global economic growth and the increased competition of homogenization, transformation and upgrading of related products are influenced. By fluorinating the chlorine on the epoxy chloropropane, the epoxy fluoropropane with more excellent product can be obtained, and compared with epoxy chloropropane, the epoxy fluoropropane has lower boiling point, more excellent thermal stability and corrosion resistance and is a good substitute of the epoxy chloropropane.

Currently, there are few reports on the synthesis of epifluoropropane. The ChemMedchem journal discloses a method for synthesizing epoxy fluoropropane by taking glycidyl p-toluenesulfonate as a starting material in 2018, wherein the starting material is expensive and not easy to obtain, can be synthesized and used only in a small amount in a laboratory, and is not suitable for industrial production.

Disclosure of Invention

In order to solve the technical problems, the invention selects cheap and easily-obtained glycerol as the starting material, and synthesizes the epoxyfluoropropane through chlorination, fluorine-chlorine exchange and Williamson cyclization.

In order to achieve the technical purpose, the invention adopts the following technical scheme:

a preparation method of epoxy fluoropropane comprises the following steps:

(1) chlorination: taking glycerol as a starting material and carboxylic acid as a catalyst, continuously introducing hydrogen chloride gas at 50-150 ℃, stopping introducing the hydrogen chloride when the reaction is finished, and performing post-treatment to obtain a product 1, 3-dichloro-2-propanol;

(2) fluorine-chlorine exchange: adding propionamide into the obtained product 1, 3-dichloro-2-propanol, simultaneously adding 1-10 times of inorganic fluoride salt in molar mass, heating to 150-250 ℃, reacting for 1-5 h, stopping the reaction, and separating to obtain 1, 3-difluoro-2-propanol;

(3) williamson cyclization: adding 1, 3-difluoro-2-propanol into a reaction kettle, adding strong base and a dispersing solvent, reacting for 1-8 h at-20-50 ℃, filtering after the reaction is finished, and rectifying to obtain the product of the epoxyfluoropropane.

The reaction chemical equation is as follows:

preferably, the carboxylic acid catalyst is one of acetic acid, adipic acid, 3-chloropropionic acid or malonic acid.

Further, the addition amount of the carboxylic acid catalyst is 2-15% of the mass of the glycerol, and the chlorination temperature is 80-120 ℃.

Preferably, the inorganic fluorine salt MF comprises one or more of sodium fluoride, potassium fluoride, ammonium fluoride, antimony trifluoride, magnesium fluoride, lead fluoride, selenium hexafluoride, mercury fluoride, lithium fluoride.

Further, the inorganic fluorine salt: the mol ratio of 1, 3-dichloro-2-propanol is 5-1: 1.

preferably, the fluorine-chlorine exchange reaction temperature is 160-220 ℃, and the reaction time is 1-3 h.

Preferably, the strong base in the Williamson cyclization includes one or more of an inorganic strong base such as sodium hydroxide, calcium hydroxide, potassium hydroxide, lithium hydroxide, or barium hydroxide, and an organic strong base or a catalyst supporting a strong base.

Further, the strong base: the molar ratio of the 1, 3-difluoro-2-propanol is 10-1.5: 1.

Preferably, the dispersion solvent is one or more of petroleum ether, toluene, cyclohexane or trifluorotoluene.

Preferably, the Williamson cyclization reaction temperature is-5-20 ℃, and the reaction time is 2-5 h.

Compared with the prior art, the invention has the following beneficial effects:

(1) the invention prepares the epoxy fluoropropane as a single product for the first time, and opens up a way for the industrial application of subsequent epoxy fluoropropane replacing epoxy chloropropane;

(2) the invention takes the cheap and easily obtained glycerin as the initial raw material to synthesize the epoxyfluoropropane, has few byproducts, high conversion rate and selectivity and higher economic benefit;

(3) the invention obtains the preparation process of the epoxy fluoropropane by exploring the preparation method of the epoxy fluoropropane, and lays a foundation for the industrial large-scale production of the epoxy fluoropropane.

(4) The preparation process is safe and controllable, green and environment-friendly, and has strong economic cyclicity.

Detailed Description

In order to enhance the understanding of the present invention, the present invention will be further described with reference to the following specific examples.

Example 1

(1) Preparation of 1, 3-dichloro-2-propanol

500g of glycerol and 25g of acetic acid are added into a 1L reaction bottle provided with a gas distributor, a condensation reflux pipe and a water separator, stirred and slowly heated to 110 ℃. Introducing hydrogen chloride gas at the speed of 0.1kg/h, starting condensation and dividing water. And introducing hydrogen chloride gas for 4 hours, stopping the reaction, and slowly cooling to the normal temperature. Aqueous sodium bicarbonate solution was added and the layers were separated. 4g of anhydrous calcium chloride was added to the organic layer, and the mixture was dried and filtered to obtain 625g of 1, 3-dichloro-2-propanol as a product with a yield of 89.1%.

(2) Preparation of 1, 3-difluoro-2-propanol

625g of 1, 3-dichloro-2-propanol obtained above was put into a 2L reaction flask, 500ml of propionamide and 420g of potassium fluoride were added thereto, and stirring and temperature rise were carried out. Heating to 180 ℃, keeping the temperature for reaction for 2 hours, stopping the reaction, and slowly cooling to normal temperature. The solid salt was removed by filtration, and the obtained reaction solution was rectified to obtain 302g of 1, 3-difluoro-2-propanol with a yield of 65.0%.

(3) Preparation of epifluoroxypropane

302g of 1, 3-difluoro-2-propanol and 500ml of petroleum ether were charged into a 1L reaction flask, cooled to 0 ℃ or lower, and stirred. 316g of ground potassium hydroxide is slowly added in batches, and the reaction temperature is controlled below 0 ℃. After the addition, the reaction was carried out at 0 ℃ for 3 hours. Filtering, washing a filter cake with petroleum ether, and rectifying the filtrate to obtain 226g of the product of the epifluoroxypropane with the yield of 94.5 percent.

Example 2

(1) Preparation of 1, 3-dichloro-2-propanol

500g of glycerol and 25g of acetic acid are added into a 1L reaction bottle provided with a gas distributor, a condensation reflux pipe and a water separator, stirred and slowly heated to 110 ℃. Introducing hydrogen chloride gas at the speed of 0.1kg/h, starting condensation and dividing water. And introducing hydrogen chloride gas for 4 hours, stopping the reaction, and slowly cooling to the normal temperature. Aqueous sodium bicarbonate solution was added and the layers were separated. 4g of anhydrous calcium chloride was added to the organic layer, and the mixture was dried and filtered to obtain 625g of 1, 3-dichloro-2-propanol as a product with a yield of 89.1%.

(2) Preparation of 1, 3-difluoro-2-propanol

625g of 1, 3-dichloro-2-propanol obtained above was put into a 2L reaction flask, 500ml of propionamide and 520g of potassium fluoride were added thereto, and stirring and temperature rise were carried out. Heating to 180 ℃, keeping the temperature for reaction for 2 hours, stopping the reaction, and slowly cooling to normal temperature. The solid salt was removed by filtration, and the obtained reaction solution was rectified to obtain 297g of 1, 3-difluoro-2-propanol with a yield of 63.9%.

(3) Preparation of epifluoroxypropane

Into a 1L reaction flask were added 297g of 1, 3-difluoro-2-propanol and 500ml of petroleum ether, and the mixture was cooled to a temperature of-10 ℃ or lower and stirred. 316g of ground potassium hydroxide is slowly added in batches, and the reaction temperature is controlled below-10 ℃. After the addition, the reaction is carried out for 5 hours at the temperature of minus 10 ℃. Filtering, washing a filter cake with petroleum ether, and rectifying the filtrate to obtain 222g of the product of the epifluoroxypropane with the yield of 94.3 percent.

Example 3

(1) Preparation of 1, 3-dichloro-2-propanol

500g of glycerol and 40g of adipic acid are added into a 1L reaction bottle provided with a gas distributor, a condensation reflux pipe and a water separator, stirred and slowly heated to 120 ℃. Introducing hydrogen chloride gas at the speed of 0.1kg/h, starting condensation and dividing water. And introducing hydrogen chloride gas for 4 hours, stopping the reaction, and slowly cooling to the normal temperature. Aqueous sodium bicarbonate solution was added and the layers were separated. 4g of anhydrous calcium chloride was added to the organic layer, and the mixture was dried and filtered to obtain 642g of 1, 3-dichloro-2-propanol as a product in a yield of 91.5%.

(2) Preparation of 1, 3-difluoro-2-propanol

642g of 1, 3-dichloro-2-propanol obtained above was put into a 2L reaction flask, 500ml of propionamide and 310g of sodium fluoride were added thereto, and the mixture was stirred and heated. Heating to 180 ℃, keeping the temperature for reaction for 2 hours, stopping the reaction, and slowly cooling to normal temperature. The solid salt was removed by filtration, and the obtained reaction solution was rectified to obtain 309g of 1, 3-difluoro-2-propanol with a yield of 64.7%.

(3) Preparation of epifluoroxypropane

309g of 1, 3-difluoro-2-propanol and 500ml of toluene were added to a 1L reaction flask, cooled to 10 ℃ or lower, and stirred. 226g of finely ground sodium hydroxide are slowly added in portions, and the reaction temperature is controlled below 10 ℃. After the addition, the reaction was carried out at 10 ℃ for 3 hours. Filtering, washing a filter cake with toluene, and rectifying the filtrate to obtain 233g of the product of the epifluoroxypropane with the yield of 95.2 percent.

Example 4

(1) Preparation of 1, 3-dichloro-2-propanol

500g of glycerol and 25g of 3-chloropropionic acid are added into a 1L reaction bottle provided with a gas distributor, a condensation reflux pipe and a water separator, stirred and slowly heated to 120 ℃. Introducing hydrogen chloride gas at the speed of 0.1kg/h, starting condensation and dividing water. And introducing hydrogen chloride gas for 4 hours, stopping the reaction, and slowly cooling to the normal temperature. Aqueous sodium bicarbonate solution was added and the layers were separated. 4g of anhydrous calcium chloride was added to the organic layer, and the mixture was dried and filtered to obtain 437g of 1, 3-dichloro-2-propanol as a product in a yield of 62.3%.

(2) Preparation of 1, 3-difluoro-2-propanol

437g of 1, 3-dichloro-2-propanol obtained above was put in a 2L reaction flask, 500ml of propionamide and 300g of ammonium fluoride were added thereto, and the mixture was stirred and heated. Heating to 160 ℃, keeping the temperature for reaction for 2 hours, stopping the reaction, and slowly cooling to normal temperature. The solid salt was removed by filtration, and the obtained reaction solution was rectified to obtain 213g of 1, 3-difluoro-2-propanol with a yield of 65.6%.

(3) Preparation of epifluoroxypropane

213g of 1, 3-difluoro-2-propanol and 400ml of cyclohexane were charged into a 1L reaction flask, cooled to 10 ℃ or lower, and stirred. 410g of ground calcium hydroxide was slowly added in portions, and the reaction temperature was controlled to 10 ℃ or lower. After the addition, the reaction was carried out at 10 ℃ for 3 hours. Filtering, washing a filter cake by using cyclohexane, and rectifying filtrate to obtain 136g of the product of the epoxy fluoropropane with the yield of 80.7 percent.

Example 5

(1) Preparation of 1, 3-dichloro-2-propanol

500g of glycerol and 40g of adipic acid are added into a 1L reaction bottle provided with a gas distributor, a condensation reflux pipe and a water separator, stirred and slowly heated to 120 ℃. Introducing hydrogen chloride gas at the speed of 0.1kg/h, starting condensation and dividing water. And introducing hydrogen chloride gas for 4 hours, stopping the reaction, and slowly cooling to the normal temperature. Aqueous sodium bicarbonate solution was added and the layers were separated. 4g of anhydrous calcium chloride is added into the organic layer, and the mixture is dried and filtered to obtain 633g of 1, 3-dichloro-2-propanol with the yield of 90.3 percent.

(2) Preparation of 1, 3-difluoro-2-propanol

633g of 1, 3-dichloro-2-propanol obtained above was put into a 2L reaction flask, and 500ml of propionamide and 430g of amine fluoride were added thereto, followed by stirring and warming. Heating to 160 ℃, keeping the temperature for reaction for 2 hours, stopping the reaction, and slowly cooling to normal temperature. The solid salt was removed by filtration, and the obtained reaction solution was rectified to obtain 310g of 1, 3-difluoro-2-propanol with a yield of 65.8%.

(3) Preparation of epifluoroxypropane

To a 1L reaction flask were added 310g of 1, 3-difluoro-2-propanol and 500ml of toluene, and the mixture was cooled to 10 ℃ or below and stirred. 513g of ground calcium hydroxide is slowly added in batches, and the reaction temperature is controlled below 10 ℃. After the addition, the reaction was carried out at 10 ℃ for 3 hours. Filtering, washing a filter cake with toluene, and rectifying the filtrate to obtain 226g of the product of the epoxy fluoropropane with the yield of 92.1 percent.

The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the invention has been described in detail with reference to the foregoing illustrative embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the spirit and scope of the technical solutions of the embodiments of the present invention.