阅读说明：本技术 一种1,3-丙烷磺酸内酯甲基氟代衍生物及其制备方法和应用 (1, 3-propane sultone methyl fluoro derivative and preparation method and application thereof ) 是由 杨彭君 宋朝阳 杨磊 石国林 于 2021-06-16 设计创作，主要内容包括：本发明涉及一种1,3-丙烷磺酸内酯甲基氟代衍生物的制备方法,其包括如下步骤：1)以3-丁烯-2-醇和亚硫酸氢钠为原料,以过氧化物为引发剂,在氨水溶液中发生加成反应,充分反应后,减压并加热浓缩至物料粘稠用浓盐酸酸化,冷至室温后过滤并浓缩滤液至粘稠,浓缩后的滤液转至真空反应釜中,高温真空条件下连续闪蒸脱水环化,粗品精馏处理,即得3-甲基-PS；2)甲基氟代衍生物的制备：将3-甲基-PS与二氯甲烷充分混合,加入氟化剂,充分反应后,减压脱除二氯甲烷,即得。优点为,成功制备了3-甲基-PS,其可直接被氟化处理,产物结构明确、单一,无副产物,该甲基氟代衍生物用作锂电池电解液添加剂对锂电池性能增强作用明显。(The invention relates to a preparation method of a 1, 3-propane sultone methyl fluoro derivative, which comprises the following steps: 1) taking 3-butene-2-alcohol and sodium bisulfite as raw materials, taking peroxide as an initiator, performing addition reaction in an ammonia water solution, after full reaction, decompressing, heating and concentrating until the materials are viscous, acidifying with concentrated hydrochloric acid, cooling to room temperature, filtering, concentrating the filtrate until the filtrate is viscous, transferring the concentrated filtrate into a vacuum reaction kettle, continuously performing flash evaporation, dehydration and cyclization under the condition of high temperature and vacuum, and rectifying the crude product to obtain 3-methyl-PS; 2) preparation of methyl fluoro derivative: and fully mixing the 3-methyl-PS and dichloromethane, adding a fluorinating agent, fully reacting, and removing the dichloromethane under reduced pressure to obtain the compound. The method has the advantages that the 3-methyl-PS is successfully prepared, the product can be directly fluorinated, the structure of the product is clear and single, no by-product is generated, and the methyl fluoro derivative used as the lithium battery electrolyte additive has obvious effect of enhancing the performance of the lithium battery.)

1. A preparation method of 1, 3-propane sultone methyl fluoro derivative is characterized by comprising the following steps:

1) preparation of 3-methyl-1, 3-propane sultone: taking 3-butene-2-alcohol and sodium bisulfite as raw materials, taking peroxide as an initiator, carrying out addition reaction in an ammonia water solution, after full reaction, decompressing, heating and concentrating until the materials are viscous, acidifying with concentrated hydrochloric acid, cooling to room temperature, filtering, concentrating the filtrate until the filtrate is viscous, transferring the concentrated filtrate into a vacuum reaction kettle, continuously carrying out flash evaporation, dehydration and cyclization under the high-temperature vacuum condition to obtain a crude product, and carrying out rectification treatment to obtain 3-methyl-1, 3-propane sultone;

2) preparation of methyl fluoro derivative: fully mixing 3-methyl-1, 3-propane sultone with dichloromethane, then adding a fluorinating agent, fully reacting, and removing the dichloromethane under reduced pressure to obtain the 1, 3-propane sultone methyl fluoro derivative.

2. The method for preparing the 1, 3-propane sultone methyl fluoro derivative according to claim 1, wherein the molar ratio of the 3-buten-2-ol to the sodium bisulfite in step 1) is 1: 1.2-1.5.

3. The method for preparing 1, 3-propane sultone methyl fluoro derivative of claim 1, wherein the peroxide in step 1) is tributyl hydroperoxide or hydrogen peroxide.

4. The method for preparing the 1, 3-propane sultone methyl fluoro derivative according to claim 1, wherein the molar ratio of the initiator to the 3-buten-2-ol in the step 1) is 0.05 to 0.08: 1.

5. the process according to claim 1, wherein the concentration of the aqueous ammonia solution in step 1) is 10 to 20 wt%, and the molar ratio of ammonia to 3-buten-2-ol used in the aqueous ammonia solution in step 1) is 0.2 to 0.5: 1.

6. the method for preparing 1, 3-propane sultone methyl fluoro derivative as claimed in claim 1, wherein the reaction temperature of step 1) in ammonia water solution is controlled at 45-50 deg.C, the reaction time is 10-15h, the concentration of concentrated hydrochloric acid used for acidification is 30-35 wt%, the temperature of concentrated hydrochloric acid for acidification is controlled at 45-60 deg.C, the temperature of continuous flash evaporation dehydration cyclization is controlled at 145-150 deg.C, and the vacuum degree is controlled at 1-10mm Hg.

7. The process for producing a 1, 3-propanesultone methylfluoro derivative as claimed in claim 1, wherein the 3-methyl-1, 3-propanesultone is mixed with methylene chloride in the step 2) in a ratio of 1mol:400-1000 mL.

8. The method for preparing a 1, 3-propane sultone methyl fluoro derivative according to any of claims 1 to 7, characterized in that the fluorinating agent in step 2) is hydrogen fluoride gas and the ratio of hydrogen fluoride to the total amount of the fluorinated derivative is 1: 3-5 by volume, and the molar ratio of the fluorinating agent to the 3-methyl-1, 3-propane sultone is 0.5-1: 1, during the fluorination reaction, the pressure is controlled to be normal pressure, and the reaction temperature is 25-40 ℃.

9. A 1, 3-propane sultone methyl fluoro derivative, prepared by the process of any one of claims 1 to 8.

10. Use of the 1, 3-propane sultone methylfluoro derivative of claim 9 as an additive for lithium battery electrolytes.

Technical Field

The invention belongs to the field of chemical industry, and particularly relates to a 1, 3-propane sultone methyl fluoro derivative, and a preparation method and application thereof.

Background

1, 3-propane sultone (PS or 1,3-PS for short) belongs to a novel functional fine chemical material. It can react with many kinds of compounds under very mild condition to provide sulfonic acid group accurately, so that it is excellent general sulfonating agent and important medicine intermediate.

PS and derivatives thereof are proved to be better additives of lithium battery electrolyte at present, which are beneficial to improving the cycle life and high-temperature performance of the battery and inhibiting gas generation, wherein fluorine-substituted PS derivatives are more particularly beneficial to improving the safety of the battery because fluorine has a negative film forming effect and a flame retardant effect.

The existing fluorinated derivatives of PS are generally prepared by directly fluorinating with hydrogen fluoride gas in an organic solvent or by firstly halogenating (chloro-or bromo-) and then preparing under the action of a chain transfer agent and a fluorinating agent. In the two existing methods, the former method is direct fluorination and is simple, but in actual production, a fluorinating agent can act on hydrogen on carbons from 1 to 3 on a PS ester ring during fluorination substitution, so that monosubstituted PS derivatives of 1-fluoro PS, 2-fluoro PS and 3-fluoro PS are correspondingly generated, the reactivity of three carbons on the ester ring has no obvious difference, and when the fluorinating agent is introduced (for example, the whole fluorinating agent is controlled to be introduced with a molar quantity smaller than that of PS), the situation that a difluorotrifluoro-PS derivative is generated due to excessive local fluorinating agent is easy to occur, namely, the direct fluorination on the whole hardly ensures that the fluorinated product is single; the latter can ensure that the position of fluorine grafted into PS is relatively fixed and the product is relatively single by firstly halogenating and positioning and then chain transfer fluorination. The applicant researches on the fluorinated PS derivative to find that the fluorinated PS produced by the former method and the fluorinated PS produced by the latter method are added in equal proportion, and the latter has obviously better and more stable enhancement on the cycle performance of the lithium battery; meanwhile, through a halogenated positioning method, the applicant tries to prepare 1-fluorinated PS, 2-fluorinated PS and 3-fluorinated PS respectively, and inspects the influence of the additives on the performance of the lithium battery respectively, and finds that the 3-fluorinated PS has the best effect and is possibly related to the stability of the 3-fluorinated PS. Therefore, how to effectively prepare the fluorinated PS derivative with a definite structure, a single component and a carbon substitution at the 3-position as much as possible is a problem to be solved.

Disclosure of Invention

The invention aims to solve the technical problem of providing a 1, 3-propane sultone methyl fluoro derivative and a preparation method and application thereof, and aims to overcome the defects of multiple reaction steps and low yield caused by the fact that a substitution position is uncertain and product components are complex or the fluorination is completed through chain transfer after halogenation is needed in the prior art.

The technical scheme for solving the technical problems is as follows: a preparation method of 1, 3-propane sultone methyl fluoro derivative comprises the following steps:

1) preparation of 3-methyl-1, 3-propane sultone: taking 3-butene-2-alcohol and sodium bisulfite as raw materials, taking peroxide as an initiator, carrying out addition reaction in an ammonia water solution, after full reaction, decompressing, heating and concentrating until the materials are viscous, acidifying with concentrated hydrochloric acid, cooling to room temperature, filtering, concentrating the filtrate until the filtrate is viscous, transferring the concentrated filtrate into a vacuum reaction kettle, continuously carrying out flash evaporation, dehydration and cyclization under the high-temperature vacuum condition to obtain a crude product, and carrying out rectification treatment to obtain 3-methyl-1, 3-propane sultone;

2) preparation of methyl fluoro derivative: fully mixing 3-methyl-1, 3-propane sultone with dichloromethane, then adding a fluorinating agent, fully reacting, and removing the dichloromethane under reduced pressure to obtain the 1, 3-propane sultone methyl fluoro derivative.

On the basis of the above technical solutions, the present invention may further have the following further specific or preferred options.

Preferably, the molar ratio of 3-buten-2-ol to sodium bisulfite in step 1) is 1: 1.2-1.5.

Specifically, the peroxide in the step 1) is tributyl hydroperoxide or hydrogen peroxide.

Preferably, the molar ratio of initiator to 3-buten-2-ol in step 1) is from 0.05 to 0.08: 1.

preferably, the concentration of the aqueous ammonia solution in step 1) is 10 to 20% by weight, and the molar ratio of ammonia to 3-buten-2-ol used in the aqueous ammonia solution in step 1) is 0.2 to 0.5: 1.

specifically, the temperature of the reaction in the ammonia water solution in the step 1) is controlled to be 45-50 ℃, the reaction time is 10-15h, the concentration of concentrated hydrochloric acid used for acidification is 30-35 wt%, the temperature of the concentrated hydrochloric acid used for acidification is controlled to be 45-60 ℃, the temperature of the continuous flash evaporation dehydration cyclization is controlled to be 135-160 ℃, and the vacuum degree is controlled to be 1-10mm Hg.

Specifically, in the step 2), 3-methyl-1, 3-propane sultone and dichloromethane are mixed according to the proportion of 1mol:400-1000 mL.

Preferably, the fluorinating agent in step 2) is hydrogen fluoride gas and the ratio of the fluorinating agent to the hydrogen fluoride gas is 1: 3-5 volume ratio diluted by inert gas (the inert gas is nitrogen or other dry pure gas which does not participate in the reaction), and the molar ratio of the fluorinating agent to the 3-methyl-1, 3-propane sultone is 0.5-1: 1, during the fluorination reaction, the pressure is controlled to be normal pressure, the reaction temperature is 25-40 ℃, and the reaction time is 1-3 h.

The invention also provides application of the 1, 3-propane sultone methyl fluoro derivative, which is used as an additive of a lithium battery electrolyte.

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

the method successfully prepares the 3-methyl-1, 3-propane sultone (3-methyl-PS), and then directly uses a fluorinating agent to perform fluorination treatment on the product to obtain the 1, 3-propane sultone methyl fluoro derivative (3-fluoro-3-methyl-1-propane sultone), wherein the fluorinated product has a definite and single structure and no by-product, and the methyl fluoro derivative of the PS is used as a lithium battery electrolyte additive, has obvious effect of enhancing the performance of a lithium battery and is better than that of the single fluorine substituted PS produced by the conventional method. The 3-methyl-PS prepared firstly enables the carbon No. 3 on an ester ring to become tertiary carbon, the hydrogen reaction activity on the tertiary carbon is enhanced, when the fluorinating agent is subjected to fluorination treatment, fluorine can more easily replace hydrogen atoms on the carbon No. 3, the reaction condition is mild, the reaction speed is high, the position of fluorination substitution is definite, the defects that the substitution position is not definite when the fluorination is directly carried out, the components of fluoro products are complex, and the defects that the route is long, the pollution is heavy and the yield is low because the fluorine is introduced by firstly halogenated positioning and then chain transfer in the prior art are overcome.

Detailed Description

The principles and features of this invention are described below in conjunction with specific embodiments, which are set forth merely to illustrate the invention and are not intended to limit the scope of the invention.

For the sake of brevity, the drugs used in the following examples are all conventional products unless otherwise specified, and the methods used are all conventional methods unless otherwise specified.

Example 1

Preparation of 3-methyl-1, 3-propane sultone:

taking 14.42g (0.2mol) of 3-butene-2-alcohol, 15.0mL of water and 0.96g of tributyl hydroperoxide, mixing and dissolving to obtain a first solution for later use; 30.00g of sodium bisulfite is mixed with 100mL of water to obtain a second solution for later use. Adding 10 wt% ammonia water solution 30mL into a reaction container, heating and controlling the temperature to be between 45-50 ℃, simultaneously dropwise adding the first solution and the second solution into the ammonia water solution, controlling the dropwise adding speed to be 1-3 drops/s, continuously keeping the temperature range after the dropwise adding is finished, continuously reacting for 10-15h, judging the reaction process by TLC, after the reaction is finished, evaporating ammonia gas under reduced pressure and simultaneously evaporating water until the material is obviously thickened, then adding 30 wt% concentrated hydrochloric acid, controlling the volume to be about 1-2 times of the volume of the material after thickening, continuously stirring and maintaining the temperature at 45-60 ℃ during acidification for 5-8h, then cooling to room temperature, filtering to remove precipitated salts such as sodium chloride, evaporating and concentrating the filtrate, transferring the concentrated filtrate into a vacuum reaction kettle, vacuumizing to 1-10mmHg, heating to 145-150 ℃, and (3) continuously carrying out flash evaporation, dehydration and cyclization for about 8 hours to obtain a crude product, and carrying out conventional rectification treatment and purification on a fine product in rectification equipment to obtain 18.59g of 3-methyl-1, 3-propane sultone, wherein the total yield is 68.3%, the purity is 99.6%, and the water content is 16 ppm.

Example 2

Preparation of 3-methyl-1, 3-propane sultone:

taking 14.42g of 3-butene-2-ol, 15.0mL of water and 1.44g of tributyl hydroperoxide, mixing and dissolving to obtain a first solution for later use; and mixing 28.50g of sodium bisulfite with 100mL of water to obtain a second solution for later use. Adding 15mL of 15 wt% ammonia water solution into a reaction container, heating and controlling the temperature to be between 45 and 50 ℃, simultaneously dropwise adding the first solution and the second solution into the ammonia water solution, controlling the dropwise adding speed to be between 1 and 3 drops/s, continuously keeping the temperature range after the dropwise adding is finished, continuously reacting for 10 to 15 hours, judging the reaction process by TLC, evaporating ammonia gas under reduced pressure after the reaction is finished, simultaneously evaporating water until the material is obviously thickened, then adding 35 wt% concentrated hydrochloric acid, controlling the volume to be about 1 to 2 times of the volume of the material after the thickening, continuously stirring and maintaining the temperature at 45 to 60 ℃ for 5 to 8 hours during acidification, then cooling to room temperature, filtering to remove salts such as precipitated sodium chloride and the like, evaporating and concentrating the filtrate, transferring the concentrated filtrate into a vacuum reaction kettle, vacuumizing to 1 to 10mmHg, heating to 145-150 ℃, and (3) continuously carrying out flash evaporation, dehydration and cyclization for about 8 hours to obtain a crude product, and carrying out conventional rectification treatment and purification on a fine product in rectification equipment to obtain 18.10g of 3-methyl-1, 3-propane sultone, wherein the total yield is 66.5%, the purity is 99.8%, and the water content is 18 ppm.

Example 3

Preparation of 3-methyl-1, 3-propane sultone:

taking 14.42g of 3-butene-2-ol, 15.0mL of water and 0.42g of hydrogen peroxide, mixing and dissolving to obtain a first solution for later use; and mixing 25.00g of sodium bisulfite with 100mL of water to obtain a second solution for later use. Adding 20mL of 20 wt% ammonia water solution into a reaction container, heating and controlling the temperature to be between 45 and 50 ℃, simultaneously dropwise adding the first solution and the second solution into the ammonia water solution, controlling the dropwise adding speed to be between 1 and 3 drops/s, continuously keeping the temperature range after the dropwise adding is finished, continuously reacting for 10 to 15 hours, judging the reaction process by TLC, evaporating ammonia gas under reduced pressure after the reaction is finished, simultaneously evaporating water until the material is obviously thickened, then adding 30 wt% concentrated hydrochloric acid, controlling the volume to be about 1 to 2 times of the volume of the material after the thickening, continuously stirring and maintaining the temperature at 45 to 60 ℃ for 5 to 8 hours during acidification, then cooling to room temperature, filtering to remove salts such as precipitated sodium chloride and the like, evaporating and concentrating the filtrate, transferring the concentrated filtrate into a vacuum reaction kettle, vacuumizing to 1 to 10mmHg, heating to 145-150 ℃, and (3) continuously carrying out flash evaporation, dehydration and cyclization for about 8 hours to obtain a crude product, and carrying out conventional rectification treatment and purification on a fine product in rectification equipment to obtain 17.89g of 3-methyl-1, 3-propane sultone, wherein the total yield is 65.7%, the purity is 99.6%, and the water content is 16 ppm.

In each of the following examples, the 3-methyl-1, 3-propane sultone prepared in example 1 was used as a starting material.

Example 4

Placing 5.0g of 3-methyl-1, 3-propane sultone and 15mL of dichloromethane in a closed reaction container, fully mixing, continuously and circularly blowing hydrogen fluoride and nitrogen gas 1: 3 (after the hydrogen fluoride gas which needs to be used in total is mixed with the nitrogen gas in a corresponding proportion, the mixture is continuously blown in through a circulating pipeline, and the diluted fluorinating agent can better control the reaction severity, so that the liquid sultone is always excessive relative to the hydrogen fluoride at any moment, and a polyfluoro substituted by-product generated due to excessive local hydrogen fluoride in a system is avoided), wherein the total using amount of the hydrogen fluoride gas is 0.034mol, the reaction pressure is kept at normal pressure, the reaction temperature is 25-30 ℃, the reaction is continuously carried out for 3 hours, after the reaction is finished, dichloromethane is distilled off under reduced pressure, and the 1, 3-propane sultone methyl fluoro derivative (3-fluoro-3-methyl-1-propane sultone) is obtained by rectification treatment, wherein the total yield is 74.9%, the purity is 99.5%, and the water content is 18 ppm.

Example 5

Placing 5.0g of 3-methyl-1, 3-propane sultone and 15mL of dichloromethane in a closed reaction container, fully mixing, continuously and circularly blowing hydrogen fluoride and nitrogen gas 1: 4, keeping the total amount of hydrogen fluoride gas at 0.034mol, keeping the pressure at normal pressure, keeping the reaction temperature at 35-40 ℃ (a solvent condensation reflux device can be arranged), continuously reacting for 1h, after the reaction is finished, evaporating dichloromethane under reduced pressure, and rectifying to obtain 4.10g of 1, 3-propane sultone methyl fluoro derivative (3-fluoro-3-methyl-1-propane sultone), wherein the total yield is 72.5%, the purity is 99.6%, and the water content is 18 ppm.

Example 6

Placing 5.0g of 3-methyl-1, 3-propane sultone and 15mL of dichloromethane in a closed reaction container, fully mixing, continuously and circularly blowing hydrogen fluoride and nitrogen gas 1: 5, keeping the total amount of hydrogen fluoride gas at 0.034mol, keeping the pressure at normal pressure and the reaction temperature at 30-35 ℃, continuously reacting for 1.5h, after the reaction is finished, evaporating dichloromethane under reduced pressure, and rectifying to obtain 4.36g of the 1, 3-propane sultone methyl fluoro derivative (3-fluoro-3-methyl-1-propane sultone), wherein the total yield is 77.0%, the purity is 99.8%, and the water content is 18 ppm.

The 3-fluoro-3-methyl-1-propane sultone prepared in example 4 is used as an additive of a lithium battery electrolyte, the addition amount is 1.2 wt%, and after 50 times of cycles of a corresponding lithium battery at 65 ℃, multiple sets of tests are simultaneously carried out to avoid accidents, and the results show that the battery capacity is kept between 92% and 95%, while the battery capacity of the lithium battery prepared by the existing method of firstly carrying out chlorine or bromine halogenation positioning and then introducing fluorine by chain transfer is between 85% and 90% under the same test conditions, and the battery capacity of the lithium battery without the additive is between 75% and 82% under the same test conditions. The results show that the 3-fluoro-3-methyl-1-propane sultone provided by the invention can be used as an additive of a lithium battery electrolyte to well improve the high-temperature cycle performance of a lithium battery.

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, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.