CN112759539B - Preparation method of N, N-dimethylpyrrolidinium hexafluorophosphate - Google Patents
Preparation method of N, N-dimethylpyrrolidinium hexafluorophosphate Download PDFInfo
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- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/06—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with radicals, containing only hydrogen and carbon atoms, attached to ring carbon atoms
Abstract
The invention discloses a preparation method of N, N-dimethylpyrrolidinium hexafluorophosphate, which comprises the steps of respectively dissolving N, N-dimethylpyrrolidinium ion salt DMP-R by adopting the same organic solvent1With hexafluorophosphates R2‑PF6Is configured as DMP-R1Organic solution and R2‑PF6Organic solution of at least one of R2‑PF6Adding DMP-R dropwise into the organic solution1Stirring the organic solution for reaction, wherein the organic solvent is selected from methanol or acetonitrile; wherein R is1Is selected from F‑、Cl‑、Br‑、BF4 ‑One of (1); r2Selected from Li+、Na+、K+、NH4 +One of (1); secondly, obtaining reaction liquid after the reaction is finished and purifying the reaction liquid to obtain DMP-PF6A crude product; three, DMP-PF6The crude product is dried in vacuum to obtain DMP-PF6And (5) producing the product. The invention has the advantages that: the product prepared by the method has good quality, high yield and relatively simple process flow, and can be recycled to further improve the yield.
Description
Technical Field
The invention relates to the technical field of preparation of electrolyte salt in a super capacitor.
Background
A supercapacitor is a novel energy storage device that stores energy through an interfacial double layer formed between an electrode and an electrolyte. In recent years, the super capacitor has been industrialized, and the electrochemical device capable of storing high energy has been widely used. At present, the super capacitor has outstanding performance in providing electric power for the hybrid electric vehicle. The electrolyte of the super capacitor has important influence on the aspects of power density, energy density, service life and the like of the super capacitor, so the research and development and application of novel electrolyte salt are widely concerned. Wherein N, N-dimethylpyrrolidinium hexafluorophosphate (DMP-PF)6) Structure ofThe electrolyte is very stable, is not decomposed at the high temperature of 150 ℃ and is not decomposed when meeting water, is easier to store compared with the traditional lithium hexafluorophosphate, has longer effective period and has the advantages of the traditional hexafluorophosphate, thereby effectively improving the voltage resistance of the electrolyte and improving the energy density and the cycle performance. Simultaneous DMP-PF6Also has the traditional capacitor additive DMP-BF4The advantages of (1) can effectively improve the conductivity of the capacitor and reduce the internal resistance and the gas production of the capacitor, so that the DMP-PF (dimethyl formamide-propylene) can be used as a power supply6Has wide market prospect.
Patent application CN 108147937A discloses a preparation method of quaternary ammonium salt, and discloses that N-methyl pyrrole hexafluorophosphate, dimethyl carbonate and methanol are added into an autoclave, the reaction is carried out at the high temperature of 145 ℃ for 9 hours, then cooling crystallization is carried out, crude products are obtained by suction filtration and then are recrystallized by methanol, and finished products are obtained by filtering and drying, the yield is only 84.1 percent, the contents of metal ions K +, Na + and halogen ions are high, the reaction involves high temperature and high pressure, and the operation is dangerous.
Therefore, it is necessary to develop a DMP-PF with good selectivity, high product purity and low acid value6The preparation method of (1).
Disclosure of Invention
The purpose of the invention is: the preparation method of the N, N-dimethylpyrrolidinium hexafluorophosphate is simple and good in selectivity, and the prepared product is high in purity, low in acid value and halogen content, low in metal ion content and high in yield.
In order to achieve the purpose, the invention adopts the technical scheme that: the preparation method of the N, N-dimethylpyrrolidinium hexafluorophosphate comprises the following steps: firstly, respectively dissolving N, N-dimethylpyrrolidinium ion salt DMP-R by adopting the same organic solvent1With hexafluorophosphates R2-PF6Is configured as DMP-R1Organic solution and R2-PF6Organic solution of at least one of R2-PF6Adding DMP-R dropwise into the organic solution1And stirring the organic solution for reaction, wherein the organic solvent is selected from methanol or acetonitrile. The prepared solution is fed to ensure that reactants are fully contacted, thereby ensuring that the reaction is full,effectively improving the reaction efficiency. The reaction principle is as follows:
wherein R is1Is selected from F-、Cl-、Br-、BF4 -One of (1); r2Selected from Li+、Na+、K+、NH4 +One of (1);
secondly, obtaining reaction liquid after the reaction is finished; after the reaction liquid is concentrated and part of organic solvent is removed, HF content is detected, a proper amount of calcium formate is added according to the detection value to remove acid, and DMP-PF is obtained through filtration and separation6Organic solution, DMP-PF6Recrystallizing and purifying the organic solution to obtain DMP-PF6A crude product; or removing the organic solvent from the reaction solution to obtain a solid mixture, washing the solid mixture to remove the byproduct to obtain DMP-PF6Crude product of the previous run, DMP-PF6Drying the crude product, detecting HF content, dissolving DMP-PF with acetonitrile6Preparing DMP-PF from crude product of previous step6Adding a proper amount of calcium formate to remove acid according to the detected HF content value in the acetonitrile solution of the former crude product, filtering, and recrystallizing the filtrate to obtain DMP-PF6A crude product; or removing organic solvent from the reaction solution to obtain solid mixture, adding acetonitrile into the solid mixture, and filtering to obtain DMP-PF6Detecting HF content in organic solution, adding appropriate amount of calcium formate to remove acid according to HF content detection value, concentrating, recrystallizing and purifying to obtain DMP-PF6A crude product;
three, DMP-PF6The crude product is dried in vacuum to obtain DMP-PF6And (5) producing the product.
Further, the aforementioned process for producing N, N-dimethylpyrrolidinium hexafluorophosphate, wherein DMP-R1And R2-PF6The charging molar ratio of (a) to (b) is 1: 1.
Further, the aforementioned method for preparing N, N-dimethylpyrrolidinium hexafluorophosphate, wherein, in the first step, DMP-R is prepared1The mass fraction of the organic solution is 20% +/-5%, and the prepared R2-PF6The mass fraction of the organic solution is 20 percent±5％。
Further, the aforementioned process for producing N, N-dimethylpyrrolidinium hexafluorophosphate, wherein R is2-PF6The temperature during dissolution is controlled to be less than 25 ℃, wherein LiPF6The temperature during dissolution was controlled below 10 ℃. R2-PF6Has poor stability, and the LiPF solution temperature is not more than 25 DEG C6When dissolving, the temperature needs to be controlled not to exceed 10 ℃ to prevent LiPF6And (5) decomposing.
Further, the aforementioned process for producing N, N-dimethylpyrrolidinium hexafluorophosphate, wherein DMP-R1The temperature is controlled between 10 ℃ and 70 ℃ during the dissolution, and DMP-R1The temperature was controlled at 60 ℃. + -. 5 ℃ upon dissolution in methanol. DMP-R at about 60 deg.C1Can be dissolved well in methanol.
Further, in the method for preparing the N, N-dimethylpyrrolidinium hexafluorophosphate, in the second step, the recrystallization temperature is controlled to be-40 ℃ to-5 ℃.
Further, in the preparation method of the N, N-dimethylpyrrolidinium hexafluorophosphate, in the third step, the drying temperature is 50-140 ℃, and the vacuum degree is-0.1-0 MPa.
Further, in the preparation method of the N, N-dimethylpyrrolidinium hexafluorophosphate, the reaction temperature is controlled to be 0-80 ℃.
The invention has the advantages that: the preparation method of the N, N-dimethylpyrrolidinium hexafluorophosphate is simple, the process route is simple, the separation and the purification are easy, and the prepared product has high purity, low acid value, low moisture, less metal impurities, less halogen content and high yield. Effectively reducing the acid value and halogen content of the product can improve the electrical property of the battery.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1: at 25 deg.C, 1145g acetonitrile was added into a 2L reaction apparatus, and DMP-BF was added under stirring4(299g, 1.6mol) to prepare DMP-BF with the mass fraction of 20 percent4Acetonitrile solution. At 5 ℃ under reduced pressure LiPF6(243g, 1.6mol) was added to 972g of acetonitrile to prepare a 20% mass fraction LiPF6Acetonitrile solution. In LiPF6Adding DMP-BF dropwise into acetonitrile solution4And (3) controlling the reaction temperature of the acetonitrile solution at 20-30 ℃, and stirring for reaction for 1 h.
Secondly, after the reaction is finished, 1529g of acetonitrile is removed by concentration at 80 ℃ to obtain 980g of acetonitrile solution containing a crude product, and the HF content is detected: 350ppm, the electrical property of the battery is reduced when the acid value is higher, 1.1g of calcium formate is added and stirred to generate trace calcium fluoride, and the filtrate is obtained by filtration. The filtrate was crystallized at-25 ℃ and filtered to give the crude product.
Thirdly, drying the crude product at 100 ℃ and-0.09 Mpa for 8h to obtain 295g of a finished product, wherein the yield is 75%, the IC purity is 99.6%, and the HF content is as follows: 2.5ppm and 11ppm of water. The metal ion content was measured by ICP and the results are shown in Table 1.
Table 1:
| Al(ppm) | Ca(ppm) | Cr(ppm) | Cu(ppm) | Fe(ppm) | K(ppm) | Na(ppm) | Ni(ppm) |
| 0.02 | 0.01 | 0.03 | 0.11 | 0.15 | 2.6 | 1.9 | 0.3 |
| Pb(ppm) | Zn(ppm) | ||||||
| / | / |
the crystallization mother liquor contains trace amount of formic acid, and acetonitrile with low acid value can be obtained by rectification and reused for dissolving DMP-BF4And LiPF6Thereby achieving the purposes of recycling and reducing the industryThe purpose of reducing the cost.
From example 1 it is possible to obtain: reacting N, N-dimethylpyrrolidinium ion salt with hexafluorophosphate in acetonitrile, concentrating to remove acetonitrile after the reaction is finished, adding calcium formate to remove acid, filtering to remove precipitate, crystallizing the solution at low temperature, filtering, separating and drying to obtain the finished product. The preparation method is simple, the process route is simple, the separation and purification are easy, the prepared product has high purity, low acid value and water content and low content of halogen ions and metal ions, the defect is that the yield is not high, and the product yield can be greatly improved after the crystallization liquid is recycled and reused.
Example 2: 1155g of methanol is added into a 2L reaction device at the temperature of 30 ℃, and DMP-BF is added under the stirring state4(299g, 1.6mol), and dissolving at 60 ℃ under heat preservation to prepare DMP-BF with the mass fraction of 20%4Methanol solution. At 8 ℃ under reduced pressure LiPF6(243g, 1.6mol) was added to 972g of methanol to prepare a 20% by mass LiPF6Methanol solution. In LiPF6Dropwise adding hot DMP-BF into methanol solution4Stirring the methanol solution to react for 1h, and controlling the reaction temperature to be 40-50 ℃.
Secondly, after the reaction is finished, methanol is removed by vacuum rotary evaporation at 100 ℃ and-0.1 Mpa to obtain 550g of DMP-PF6And LiBF4And (3) solid mixture. Washing with 600g of methanol for 1h, dissolving LiBF4Filtering to obtain DMP-PF6And (5) crude product.
Three, DMP-PF6The crude product is dried in vacuum at 100 ℃ and-0.1 Mpa for 8 hours to obtain 375g of finished product, the yield is 95.7%, the IC purity is 99.2%, and the HF content: 165ppm, water content 2.5 ppm. ICP measures the metal ion content and the results are shown in Table 2.
Table 2:
| Al(ppm) | Ca(ppm) | Cr(ppm) | Cu(ppm) | Fe(ppm) | K(ppm) | Na(ppm) | Ni(ppm) |
| 0.05 | 0.03 | / | 0.11 | 0.15 | 3.6 | 2.8 | / |
| Pb(ppm) | Zn(ppm) | ||||||
| / | / |
the obtained product DMP-PF6The electrical property of the battery is influenced by the higher acid value, the obtained 375g of product is added with 562g of acetonitrile to prepare a 40% acetonitrile solution, 0.22g of calcium formate is added, the solution is stirred for 1h, the generated precipitated calcium fluoride is filtered out, the residual acetonitrile is removed by vacuum rotary evaporation at 100 ℃ to obtain 380g of solid, 400g of ethanol is added for washing for 1h, the residual formic acid is removed, the solid 375g is obtained by filtration, vacuum drying is carried out at 100 ℃ for 8h to obtain 358g of finished product, the total yield is 91.3%, and the IC purity: 99.9%, HF content: 0.5ppm, moisture: 2 ppm.
The product prepared by the method has high purity, high yield, low acid value and water content, simple process and low requirement on process equipment, and the related solvents can be recycled by rectification and purification, so the method has high industrial value.
From example 2, the following are obtained: reacting N, N-dimethylpyrrolidinium ion salt with hexafluorophosphate in methanol, heating in vacuum to remove methanol after the reaction is finished, dissolving a byproduct by using the methanol, washing a product, filtering and separating a crude product, and drying to obtain a finished product. The method has the advantages of high yield, high product purity, low water content and high acid value. But can be dissolved by acetonitrile, calcium formate is added to remove acid, and the mixture is filtered; concentrating to remove acetonitrile, washing the crude product with ethanol, separating and drying to obtain a high-quality product, and having the advantages of high yield, low acid value, more process steps and long flow.
Example 3: firstly, 870g of methanol is added into a 2L reaction device at 20 ℃, DMP-Cl (217g, 1.6mol) is added under the stirring state, and a DMP-Cl methanol solution with the mass fraction of 20% is prepared. At a temperature of 20 DEG CUnder the condition of mild reaction, NaPF6(269g, 1.6mol) was added with 1076g of methanol to prepare 20% by mass NaPF6Methanol solution. In NaPF6Dropwise adding DMP-Cl methanol solution into the methanol solution, stirring and reacting for 1h, and controlling the reaction temperature to be 20-30 ℃.
Secondly, after the reaction is finished, methanol is removed under the pressure of-0.08 Mpa at the temperature of 100 ℃ to obtain NaCl and DMP-PF6588g of acetonitrile with the water content of less than 200ppm is added into the mixed solid, and the mixed solid is stirred and dissolved for 1h to prepare acetonitrile solution with the mass fraction of 40 percent. Filtering to remove insoluble substance byproduct NaCl to obtain 980g of crude acetonitrile solution, and detecting solution HF: 305 ppm. 0.97g of calcium formate is added, stirred and deacidified for 1 hour, and filtered. The filtrate is concentrated at 100 ℃ to remove 350g of acetonitrile to obtain DMP-PF with the mass concentration of 60 percent6And (3) carrying out freezing crystallization on the acetonitrile concentrated solution at the temperature of minus 25 ℃ for 2 hours, and filtering to obtain a crude product.
Thirdly, drying the crude product at 100 ℃ under-0.1 Mpa for 8 hours to obtain finished product 366g, with the yield of 93.4%, IC purity of 99.8%, HF content: 1.3ppm, moisture: 9ppm, Cl ion content: 3.1 ppm. ICP measures the metal ion content and the results are shown in Table 3.
Table 3:
| Al(ppm) | Ca(ppm) | Cr(ppm) | Cu(ppm) | Fe(ppm) | K(ppm) | Na(ppm) | Ni(ppm) |
| / | 0.05 | 0.04 | 0.01 | 0.13 | 4.6 | 3.9 | / |
| Pb(ppm) | Zn(ppm) | ||||||
| / | 0.1 |
the product prepared by the method has high purity, high yield, low acid value and water content, low halogen ion content, low metal ion content and simple process flow.
Example 4
N, N-dimethylpyrrolidinium hexafluorophosphate (DMP-PF)6) The methanol system is synthesized, recrystallized and purified.
Firstly, 764g of methanol was added to a 2L reaction apparatus at 40 ℃, and DMP-F (191g, 1.6mol) was added under stirring to prepare a 20% by mass DMP-F methanol solution. At 15 ℃ under reduced pressure of KPF6(295g, 1.6mol) is added into 1180g of methanol to prepare KPF with the mass fraction of 20 percent6Methanol solution in KPF6Dropwise adding DMP-F methanol solution into the methanol solution, stirring and reacting for 1h, and controlling the reaction temperature to be 30-40 ℃.
Secondly, after the reaction is finished, methanol is removed at 100 ℃ and-0.1 Mpa to obtain KF and DMP-PF6Adding 588g of acetonitrile with the water content of less than 200ppm into the mixed solid, stirring and dissolving for 1h to prepare a 40% acetonitrile solution, filtering to remove insoluble substances and obtain 980g of a crude acetonitrile solution, and detecting a solution HF: 325 ppm. Adding 1g of calcium formate, stirring for deacidification for 1h, and filtering to obtain a filtrate. The filtrate is concentrated at 100 ℃ to remove 350g of acetonitrile to obtain DMP-PF with the mass concentration of 60 percent6And (3) carrying out acetonitrile concentrated solution, carrying out freezing crystallization on the concentrated solution at the temperature of-20 ℃ for 2h, and filtering to obtain a crude product.
Thirdly, drying the crude product at 100 ℃ under-0.1 Mpa for 8 hours to obtain 362g of finished product, wherein the yield is 92.3%, the IC purity is 99.7%, and the HF content is as follows: 0.9ppm, moisture: 12ppm, F ion content: 1.2 ppm. ICP measurement of metal ion content table 4.
Table 4:
| Al(ppm) | Ca(ppm) | Cr(ppm) | Cu(ppm) | Fe(ppm) | K(ppm) | Na(ppm) | Ni(ppm) |
| 0.05 | 0.03 | / | / | 0.15 | 4.6 | 3.9 | 0.3 |
| Pb(ppm) | Zn(ppm) | ||||||
| 0.3 | / |
example 5:
n, N-dimethylpyrrolidinium hexafluorophosphate (DMP-PF)6) The methanol system is synthesized, and recrystallization purification is carried out.
Firstly, at 40 ℃, 1149g of methanol is added into a 2L reaction device, and DMP-Br (288g, 1.6mol) is added into the reaction device under the stirring state to prepare a DMP-Br methanol solution with the mass fraction of 20 percent. NH is carried out at the temperature of 20 +/-5 DEG C4PF6(261g, 1.6mol) was added to 1044g of methanol to prepare 20% NH4PF6Methanol solution. At NH4PF6Dropwise adding a DMP-Br methanol solution into the methanol solution, stirring and reacting for 1h, and controlling the reaction temperature to be 50 +/-5 ℃.
Secondly, methanol is removed under the temperature of 100 ℃ and the pressure of-0.1 Mpa to obtain NH4Br and DMP-PF6Adding 565g of acetonitrile with water content less than 200ppm, stirring and dissolving for 1h to prepare acetonitrile solution with mass concentration of 40%, filtering to remove insoluble substances and obtain by-product NH4Br to give 972g of a crude acetonitrile solution, detection of the solution HF: 365ppm, adding 1.2g of calcium formate, stirring for deacidification for 1h, and filtering to obtain a filtrate. The filtrate is concentrated at 100 ℃ to remove 350g of acetonitrile to obtain 60 percent high-concentration DMP-PF6Acetonitrile solution is frozen and crystallized for 2h at minus 30 ℃ and filtered to obtain crude product.
Thirdly, drying the crude product at 100 ℃ under-0.1 Mpa for 8 hours to obtain 357g of finished product, with the yield of 91.1%, the IC purity of 99.8%, and the HF content: 0.5ppm, moisture: 5ppm, Br ion content: 2.3 ppm. The metal ion content by ICP assay is shown in Table 5.
Table 5:
| Al(ppm) | Ca(ppm) | Cr(ppm) | Cu(ppm) | Fe(ppm) | K(ppm) | Na(ppm) | Ni(ppm) |
| / | 0.01 | / | 0.11 | 0.15 | 3.6 | 1.5 | 0.3 |
| Pb(ppm) | Zn(ppm) | ||||||
| 0.4 | / |
from examples 4, 5: reacting N, N-dimethylpyrrolidinium ion salt with hexafluorophosphate in methanol, after the reaction is finished, heating in vacuum to remove the methanol to obtain a mixed solid of a crude product and a byproduct, adding acetonitrile to dissolve the product, filtering to separate the byproduct, adding calcium formate to the filtrate to remove acid, filtering out precipitates, concentrating the filtrate, crystallizing at low temperature, filtering, separating and drying to obtain a finished product. The method has the advantages of good product quality, high yield, relatively simple process flow and capability of recycling and further improving the yield.
The invention has the advantages that: the preparation method of the N, N-dimethylpyrrolidinium hexafluorophosphate is simple, the process route is simple, dangerous operations such as high temperature and high pressure do not exist, the operation is safe and simple, the obtained crude product is easy to separate and purify, the prepared product is high in purity, good in yield, low in acid value, low in moisture and low in halogen ion, and related raw materials and products are low in toxicity. The electrolyte salt, namely lithium hexafluorophosphate, often contains a large amount of hydrogen fluoride, the content of the refined hydrogen fluoride is about 150ppm, and the content of the refined hydrogen fluoride exceeds the sum of all other impurity ions by a plurality of times, and the electrical property of the battery can be greatly reduced due to the presence of the hydrogen fluoride, while the content of HF in the N, N-dimethylpyrrolidinium hexafluorophosphate prepared by the preparation method disclosed by the invention is very low, and in the embodiment, the content of HF is lower than 5ppm, so that the electrical property of the battery can be effectively improved.
The above examples are intended to illustrate several embodiments of the present invention, but do not limit the present invention to the above embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Claims (8)
- A process for the preparation of N, N-dimethylpyrrolidinium hexafluorophosphate, characterized in that: the method comprises the following steps: firstly, respectively dissolving N, N-dimethylpyrrolidinium ion salt DMP-R by adopting the same organic solvent1With hexafluorophosphates R2-PF6Is configured as DMP-R1Organic solution and R2-PF6Organic solution of at least one of R2-PF6Adding DMP-R dropwise into the organic solution1Stirring the organic solution for reaction, wherein the organic solvent is selected from methanol or acetonitrile; the reaction principle is as follows:
wherein R is1Is selected from F-、Cl-、Br-、BF4 -One of (1); r2Selected from Li+、Na+、K+、NH4 +One of (1);secondly, obtaining reaction liquid after the reaction is finished; after the reaction liquid is concentrated and part of organic solvent is removed, HF content is detected, calcium formate is added according to the detected value to remove acid, and DMP-PF is obtained by filtering and separating6Organic solution, DMP-PF6Recrystallizing and purifying the organic solution to obtain DMP-PF6A crude product; or removing the organic solvent from the reaction solution to obtain a solid mixture, washing the solid mixture to remove byproducts, and obtaining the DMP-PF6Drying the crude product, detecting HF content, dissolving DMP-PF with acetonitrile6Preparation of crude product of the previous stepDMP-PF6Adding calcium formate into acetonitrile solution of the former crude product according to the detection value of HF content to remove acid, filtering, recrystallizing the filtrate to obtain DMP-PF6A crude product; or removing organic solvent from the reaction solution to obtain a solid mixture, adding acetonitrile into the solid mixture, and filtering to obtain DMP-PF6Detecting HF content in organic solution, adding calcium formate to remove acid according to the HF content detection value, concentrating, recrystallizing and purifying to obtain DMP-PF6A crude product;three, DMP-PF6The crude product is dried in vacuum to obtain DMP-PF6And (5) producing the product. - 2. The process for the preparation of N, N-dimethylpyrrolidinium hexafluorophosphate according to claim 1, wherein: DMP-R1And R2-PF6The feeding molar ratio of (A) to (B) is 1: 1.
- 3. The process for the preparation of N, N-dimethylpyrrolidinium hexafluorophosphate according to claim 2, wherein: in the first step, the DMP-R is formulated1The mass fraction of the organic solution is 20% +/-5%, and the prepared R2-PF6The mass fraction of the organic solution is 20% +/-5%.
- 4. A process for the preparation of N, N-dimethylpyrrolidinium hexafluorophosphate according to claim 1, 2 or 3, wherein: r2-PF6The temperature during dissolution is controlled to be less than 25 ℃, wherein LiPF6The temperature during dissolution was controlled below 10 ℃.
- 5. A process for the preparation of N, N-dimethylpyrrolidinium hexafluorophosphate according to claim 1, 2 or 3, wherein: DMP-R1The temperature is controlled between 10 ℃ and 70 ℃ during the dissolution, and DMP-BF is contained in the solution4The temperature was controlled at 60 ℃. + -. 5 ℃ upon dissolution in methanol.
- 6. A process for the preparation of N, N-dimethylpyrrolidinium hexafluorophosphate according to claim 1, 2 or 3, wherein: in the second step, the recrystallization temperature is controlled to be-40 ℃ to-5 ℃.
- 7. A process for the preparation of N, N-dimethylpyrrolidinium hexafluorophosphate according to claim 1, 2 or 3, wherein: in the third step, the drying temperature is 50-140 ℃, and the vacuum degree is-0.1-0 Mpa.
- 8. A process for the preparation of N, N-dimethylpyrrolidinium hexafluorophosphate according to claim 1, 2 or 3, wherein: the reaction temperature in the first step is controlled to be 0-80 ℃.
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| N-Methyl-N-alkylpyrrolidinium Hexafluorophosphate Salts: Novel Molten Salts and Plastic Crystal Phases;J. Golding等;《Chemistry of Materials》;20010123;第558-564页 * |
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