CN111170898A - Preparation method of potassium perfluorobutane sulfonate - Google Patents
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Abstract
Discloses a method for preparing potassium perfluorobutane sulfonate, which adopts continuous fluid reaction to replace batch kettle type reaction and comprises the following steps: (i) providing a tubular reactor; (ii) continuously feeding an aqueous slurry of perfluorobutanesulfonyl fluoride and potassium hydroxide and calcium hydroxide to said tubular reactor at a reaction temperature of from 70 ℃ to 100 ℃ and a pressure sufficient to maintain perfluorobutanesulfonyl fluoride in a liquid state; (iii) drying the reaction mixture to obtain a solid containing calcium fluoride and potassium perfluorobutane sulfonate; (iv) dissolving the solid with ethanol at 65-76 deg.C; and (v) crystallizing the dissolved ethanol solution containing potassium perfluorobutane sulfonate to obtain potassium perfluorobutane sulfonate.
Description
Technical Field
The invention relates to a method for preparing potassium perfluorobutyl sulfonate through continuous reaction. The method can continuously produce the potassium perfluorobutanesulfonate, has high heating efficiency, uses the temperature higher than the boiling point of the perfluorobutanesulfonyl fluoride raw material for reaction, has low water consumption and high reaction rate, can completely convert the perfluorobutanesulfonyl fluoride raw material, has high yield, recycles the heat generated by the reaction, saves energy compared with the conventional method, solves the defects of long heating time of the conventional reaction device, incomplete conversion of the perfluorobutanesulfonyl fluoride, difficult separation of calcium fluoride byproduct precipitate, low product purity, low production efficiency and the like
Background
The potassium perfluorobutylsulfonate is an important additive used in the processing of thermoplastics, has excellent antistatic property, flame retardancy and heat resistance, can be fully combined with transparent plastic resins such as polycarbonate, polyimide, polyester, polystyrene, polyamide, polyketone, ABS and the like, does not change the inherent characteristics of substrates and also improves the transparency of the substrates, and is widely applied in the market.
"preparation of potassium perfluorobutanesulfonate by electrochemical fluorination" of Wanenren et al (organofluorine industry, No. 4 of 2003) describes a process for preparing potassium perfluorobutanesulfonate by respectively using sulfolene or butyl chloride sulfonate as raw material through processes of electrolytic fluorination and the like, the reaction equation of which is:
C4F9SO2F+2KOH→C4F9SO3K+KF+H2O
if potassium perfluorobutane sulfonate with low KF content is prepared, calcium oxide may be added to the system to convert it to calcium fluoride precipitate:
the preparation method comprises the following steps: a four-necked flask equipped with an electric stirrer, a constant pressure titrator, a reflux condenser and a thermometer was charged with a 50% aqueous solution of potassium hydroxide, calcium oxide was added to the vessel containing the aqueous solution of potassium hydroxide, and perfluorobutanesulfonyl fluoride was added dropwise while stirring until the pH was 7 to 7.5. Filtering while hot, removing calcium fluoride precipitate, and cooling the filtrate to separate out potassium perfluorobutane sulfonate crystal.
Fanchunle 'synthesis research of potassium perfluorobutanesulfonate' (organic fluorine industry, 2 nd 2005) discloses a synthesis method of potassium perfluorobutanesulfonate, which comprises adding potassium hydroxide, calcium oxide, deionized water and ethanol into an enamel kettle, slowly and continuously adding perfluorobutanesulfonyl fluoride under stirring, and reacting until the pH of the materials in the kettle is 7-7.5. Standing at 50 deg.C for 2-4 hr, collecting supernatant, centrifuging the lower layer to obtain calcium fluoride precipitate, and mixing the supernatants. Crystallizing, filtering, drying and crushing the potassium perfluorobutane sulfonate solution to obtain a finished product.
Although the existing batch kettle type preparation method has the advantages of simple and convenient synthesis process conditions, the method also has the following defects:
(i) because a large amount of perfluorobutanesulfonyl fluoride hydrolysis reaction is violent and a large amount of heat is released, the existing method emphasizes that perfluorobutanesulfonyl fluoride must be added in a 'slow dropwise mode' or a 'slow continuous mode', and sudden temperature and pressure rise of a system caused by violent reaction is avoided, so that the whole reaction process becomes long; meanwhile, as the boiling point of the perfluorobutanesulfonyl fluoride is 64 ℃ and is volatile, the perfluorobutanesulfonyl fluoride is boiled and evaporated at a temperature higher than the boiling point (70-80 ℃), a large amount of perfluorobutanesulfonyl fluoride exists in a free space of the reaction kettle, and the leakage and the waste of raw materials are easy; the reaction at a temperature lower than the above temperature also causes a small amount of perfluorobutanesulfonyl fluoride to be unreacted and mixed in the reaction system, thereby causing difficulty in subsequent separation.
(ii) After the reaction is finished, because the granularity of the calcium fluoride is too fine, the calcium fluoride is difficult to separate by filtration in the actual treatment process, and only standing layering separation can be carried out, so that the production time is prolonged, a large amount of potassium perfluorobutanesulfonate remains in the separated calcium fluoride, the potassium perfluorobutanesulfonate is difficult to remove, the product is wasted, and the purity of the calcium fluoride byproduct is influenced.
(iii) The reaction uses water as a solvent, the solubility of the water to the potassium perfluorobutane sulfonate is low, and the potassium perfluorobutane sulfonate product is easily crystallized and mixed in the calcium fluoride filtering process; the mixed solution of water and ethanol (the ethanol acts to increase the solubility of the perfluorobutanesulfonyl fluoride in the reaction system) is used as a solvent, so that the problems are caused, and the total amount of potassium perfluorobutanesulfonate contained in the solvent in the subsequent crystallization process is large, and the loss is increased; the problems finally cause the problems of low production efficiency, low product purity and the like of the existing preparation method.
Therefore, there is still a need to develop a novel process for preparing potassium perfluorobutanesulfonate, which can advantageously improve production efficiency and product purity.
Disclosure of Invention
An object of the present invention is to provide a novel process for producing potassium perfluorobutanesulfonate, which can advantageously improve the production efficiency and the product purity by using a continuous fluid reaction instead of a batch tank reaction.
Therefore, the invention relates to a method for preparing potassium perfluorobutane sulfonate by continuous reaction, which comprises the following steps:
(i) providing a tubular reactor;
(ii) simultaneously and continuously feeding perfluorobutanesulfonyl fluoride and an aqueous slurry of potassium hydroxide and calcium hydroxide into said tubular reactor at a reaction temperature of from 70 ℃ to 100 ℃ and under a pressure sufficient to maintain perfluorobutanesulfonyl fluoride in a liquid state;
(iii) drying the reaction mixture to evaporate water while leaving a solid comprising calcium fluoride and potassium perfluorobutane sulfonate;
(iv) dissolving the solid with ethanol at 65-76 deg.C; and
(v) crystallizing the dissolved ethanol solution containing the potassium perfluorobutane sulfonate to obtain the potassium perfluorobutane sulfonate.
Detailed Description
The method uses a tubular reactor as a reaction device for reacting perfluorobutanesulfonyl fluoride with potassium hydroxide and calcium hydroxide, and has the same reaction formula as the prior method, and comprises the following steps:
2C4H9SO2F+2KOH+Ca(OH)2→2C4F9SO3K+2H2O+CaF2↓
however, the invention adopts continuous tubular fluid reaction, even if the reaction temperature exceeds the boiling point of the perfluorobutanesulfonyl fluoride, the perfluorobutanesulfonyl fluoride can be ensured to be efficiently contacted with the reactant for reaction, the perfluorobutanesulfonyl fluoride is effectively prevented from being separated from the reaction system, the potassium perfluorobutanesulfonate can be continuously prepared, and the working efficiency is greatly improved.
Thus, the method of the invention comprises:
(i) providing a tubular reactor;
the tubular reactor suitable for the process of the present invention is not particularly limited, and may be a conventional tubular reactor known in the art as long as it can keep perfluorobutanesulfonyl fluoride in a liquid state at a temperature of, for example, 70 to 100 ℃. In one example of the present invention, the tubular reactor is selected from the group consisting of a tubular reactor and a coil reactor. The tube diameter and the tube length of the tubular reactor can be easily adjusted by one skilled in the art by means of capacity calculations.
(ii) Simultaneously and continuously feeding perfluorobutanesulfonyl fluoride and an aqueous slurry of potassium hydroxide and calcium hydroxide into said tubular reactor at a reaction temperature of from 70 ℃ to 100 ℃ and under a pressure sufficient to maintain perfluorobutanesulfonyl fluoride in a liquid state;
the reaction temperature employed in the process of the present invention is 70-100 deg.C, preferably 80-95 deg.C, more preferably 85-90 deg.C, preferably 86-88 deg.C.
The pressure of the reaction system of the present invention is not particularly limited as long as perfluorobutanesulfonyl fluoride is kept in a liquid state at a temperature of 70 to 100 ℃. The particular reaction system pressure can be readily determined by one of ordinary skill in the art in light of the present disclosure, the particular reaction temperature, and the tubular reactor.
In one embodiment of the invention, the pressure in the tubular reactor is from 0.10 to 0.8MPa, preferably from 0.13 to 0.6MPa, preferably from 0.15 to 0.5 MPa.
The relative amounts of perfluorobutanesulfonyl fluoride, potassium hydroxide and calcium hydroxide used for the reaction may be stoichiometric amounts, but the amount of water used needs to be reduced as much as possible on the premise of ensuring that the potassium hydroxide is dissolved in water and the calcium hydroxide becomes a slurry, so as to reduce energy loss in the subsequent drying process.
In one embodiment of the invention, potassium hydroxide and calcium hydroxide are maintained in slight excess to ensure complete conversion of perfluorobutanesulfonyl fluoride.
In one embodiment of the invention, the feed is fed with perfluorobutanesulfonyl fluoride: potassium hydroxide: calcium hydroxide: controlling the molar ratio of water to be 1: 1-1.1:0.5-0.55: 7-60, preferably controlled in the ratio of 1: 1-1.08:0.5-0.54: 8-50, and better controlled in the ratio of 1: 1-1.07:0.5-0.53: 9-45, and controlling the ratio of 1: 1-1.05:0.5-0.52: 10-40.
The method of feeding the perfluorobutanesulfonyl fluoride and the aqueous slurry of potassium hydroxide and calcium hydroxide simultaneously and continuously to the tubular reactor of the present invention is not particularly limited as long as the reaction raw materials in the reaction system at the time of feeding satisfy, for example, the stoichiometric amounts or the ratio of perfluorobutanesulfonyl fluoride in the materials: potassium hydroxide: calcium hydroxide: controlling the molar ratio of water to be 1: 1-1.1:0.5-0.55: 7-60 times.
(iii) Drying the reaction mixture to evaporate water while leaving a solid comprising calcium fluoride and potassium perfluorobutane sulfonate;
after the reaction in the tubular reactor, mixed slurry containing potassium perfluorobutanesulfonate, calcium fluoride and unreacted raw materials is obtained. The method for removing the water in the slurry is not particularly limited, and for example, a drying method may be adopted. The specific drying means is not particularly limited, and may be a drying method conventional in the art. In one embodiment of the invention, the slurry is sprayed into a drying device by using the pressure of a tubular reactor, and a solid containing calcium fluoride and potassium perfluorobutane sulfonate is obtained after removing water.
(iv) Dissolving the solid with ethanol at 65-76 deg.C;
in the present invention, the term "ethanol" means an aqueous ethanol solution having an alcohol concentration of 80 to 100% by weight, preferably 85 to 98% by weight, more preferably 88 to 95% by weight.
The method for dissolving the solid at high temperature is not particularly limited, and may be a conventional dissolving method in the art.
The dissolution temperature suitable for the method of the present invention is not particularly limited, and may be a conventional one in the art. In one embodiment of the invention, the dissolution temperature is 65 to 76 ℃, preferably 68 to 75 ℃, more preferably 70 to 73 ℃.
(v) Crystallizing the dissolved ethanol solution containing the potassium perfluorobutane sulfonate to obtain the potassium perfluorobutane sulfonate.
The method for crystallizing the ethanol-dissolved solution is not particularly limited, and may be a conventional crystallization method known in the art.
In one embodiment of the invention, the process of the invention comprises reacting perfluorobutanesulfonyl fluoride: potassium hydroxide: calcium hydroxide: 1 part of water: 1-1.1:0.5-0.55: 50 mol percent of the reaction solution. Heating the tubular reactor to 80 ℃ and stabilizing, injecting the reaction liquid and perfluorobutanesulfonyl fluoride into the tubular reactor at the same time according to a certain proportion, controlling the pressure of the reactor to be not less than 0.2MPa by controlling the outlet flow, directly spraying slurry containing perfluorobutanesulfonic acid potassium and calcium fluoride generated by the reaction into a drying device by utilizing the pressure of the reactor, gasifying water, and recycling condensed reclaimed water for recycling. Dissolving the dried solid (containing calcium fluoride and potassium perfluorobutane sulfonate) by using ethanol at the dissolving temperature of 70-75 ℃; and (3) after dissolving, preparing the high-purity potassium perfluorobutane sulfonate from the ethanol solution containing potassium perfluorobutane sulfonate through crystallization and purification equipment.
The invention eliminates a series of defects caused by batch kettle type reaction by changing the reaction form, solves the problems of low reaction speed, incomplete reaction of raw materials, low production efficiency, difficult subsequent separation of calcium fluoride and the like in the prior art, provides a continuous reaction technology by utilizing the fluid chemistry principle, solves the problems in the prior art, realizes continuous production, improves the production efficiency and the product quality, and reduces the manufacturing cost.
Examples
The present invention will be further illustrated by the following examples, but is not limited to these examples.
Comparative example 1
Perfluorobutanesulfonyl fluoride, potassium hydroxide, calcium hydroxide and water in a ratio of 1: 1.1:0.55: 50: the reaction is carried out according to the molar ratio of 8, and the specific operation process is as follows: adding 50% potassium hydroxide aqueous solution into a four-neck flask which is provided with an electric stirrer, a constant pressure titrator, a reflux condenser and a thermometer, then adding calcium oxide powder, starting stirring, maintaining the temperature of a reaction system at 70-80 ℃, slowly dropwise adding perfluorobutanesulfonyl fluoride into the reactor through the constant pressure titrator, and detecting the pH value of a reaction mixture from time to time until the pH value reaches 7-7.5. And pouring the material obtained by the reaction into a filtering device while the material is hot, filtering calcium fluoride precipitate generated by the reaction, then cooling the filtrate, separating out crystals when the potassium perfluorobutanesulfonate is insoluble in cold water, filtering the crystals, separating out the crystals, and sending the filter cake to a ventilation drying box, wherein the drying temperature is 100-120 ℃, and the obtained silvery white flaky crystal is the final product potassium perfluorobutanesulfonate.
Comparative example 2
Under the condition of room temperature, mixing and dissolving potassium hydroxide, calcium hydroxide, water and ethanol, and stirring at the rotating speed of 200 rpm; perfluorobutanesulfonyl fluoride was slowly added to the reaction solution to start a slow reaction. Perfluorobutanesulfonyl fluoride: potassium hydroxide: calcium hydroxide: water: the ethanol molar ratio is 1: 1.1:0.55: 50: 8. as the concentration of perfluorobutanesulfonyl fluoride increases, the reaction rate increases, and the temperature of the reaction solution begins to rise due to the reaction exotherm. When the addition of the perfluorobutanesulfonyl fluoride is finished, the reaction solution is automatically heated to 55 ℃, and the pH value is about 7. The temperature of the reaction solution was raised to about 64 ℃ by external heat, and unreacted perfluorobutanesulfonyl fluoride was recovered by a condenser until no distillate was produced, at which time the pH was 6 to 7. Stopping stirring, standing (the temperature is kept above 55 ℃), and layering. Separating supernatant liquid while the solution is hot, cooling (below 0 ℃) for crystallization, filtering and drying to obtain potassium perfluorobutane sulfonate with the detection purity of 98%;
comparative example 3
Mixing potassium hydroxide, calcium hydroxide and water, stirring at the rotation speed of 200rpm, and raising the temperature of the solution to about 50 ℃ (otherwise, potassium perfluorobutane sulfonate is crystallized and separated out in the reaction process). According to perfluorobutanesulfonyl fluoride: potassium hydroxide: calcium hydroxide: the water molar ratio is 1: 1.1:0.55: and (3) slowly adding the perfluorobutanesulfonyl fluoride into the reaction liquid according to the proportion of 50, starting to slowly react, increasing the reaction rate along with the increase of the concentration of the perfluorobutanesulfonyl fluoride, and starting to heat the reaction liquid due to the heat release of the reaction. When the addition of perfluorobutanesulfonyl fluoride was completed, the reaction solution was heated to 55 ℃ at which time the pH was about 7. The temperature of the reaction solution was raised to about 64 ℃ by external heat, and unreacted perfluorobutanesulfonyl fluoride was recovered by a condenser until no distillate was produced, at which time the pH was 6 to 7. Stopping stirring, standing (the temperature is kept above 55 ℃), and layering. Separating supernatant liquid while the solution is hot, cooling (below 0 ℃) for crystallization, filtering and drying to obtain the potassium perfluorobutane sulfonate with the purity of 98 percent.
Example 1
Setting the molar ratio of the reaction liquid as perfluorobutanesulfonyl fluoride: potassium hydroxide: calcium hydroxide: 1 part of water: 1.1:0.55: 50. mixing aqueous solutions of potassium hydroxide and calcium hydroxide in proportion to prepare a material A; heating a tubular reactor (the length of a reaction tube is 10 meters, the diameter of the tube is phi 8, water bath is purchased from Shanghai Sanai Rich New Material science and technology Co., Ltd.) to 80 ℃, after the tubular reactor is stabilized, injecting a material A and perfluorobutanesulfonyl fluoride into the tubular reactor according to the set molar ratio, controlling the pressure of the reactor to be 0.25MPa by controlling the flow rate of an outlet, keeping the perfluorobutanesulfonyl fluoride in a liquid state, directly spraying slurry containing the perfluorobutanesulfonic acid potassium and the calcium fluoride generated by the reaction into a drying device (the temperature of an oven is 120-160 ℃, the slurry is purchased from Shanghai Sanai Rich New Material science and technology Co., Ltd.) by using the pressure of the reaction tube, vaporizing water, and condensing and recycling the recovered water. Dissolving the dried solid (containing calcium fluoride and potassium perfluorobutane sulfonate) by using ethanol at the dissolving temperature of 75 ℃; and crystallizing the dissolved ethanol solution containing potassium perfluorobutane sulfonate to obtain the potassium perfluorobutane sulfonate.
Example 2
Referring to example 1, the reaction temperature was adjusted to 85 ℃ without changing other conditions.
Example 3
Referring to example 1, the reaction temperature was adjusted to 95 ℃ without changing other conditions.
Example 4
Referring to example 1, the reaction temperature was adjusted to 98 ℃ without changing other conditions.
TABLE 1 Potassium perfluorobutanesulfonate reaction results
| Components | Comparative example 1 | Comparative example 2 | Example 1 | Example 2 | Example 3 | Example 4 |
| Perfluorobutanesulfonyl fluoride conversion% | 98.1 | 98.3 | 100 | 100 | 100 | 100 |
| The yield of the potassium perfluorobutanesulfonate is percent | 90.2 | 85.6 | 99.2 | 99.5 | 99.4 | 99.8 |
| Purity of potassium perfluorobutanesulfonate% | 98.0 | 97.1 | 99.5 | 99.7 | 99.9 | 99.8 |
The results of the comparative and example product tests show (see table above): the method for preparing the potassium perfluorobutane sulfonate has the advantages of obviously improved purity and obvious reaction effect.
Claims (8)
1. A preparation method of potassium perfluorobutane sulfonate comprises the following steps:
(i) providing a tubular reactor;
(ii) continuously feeding perfluorobutanesulfonyl fluoride and an aqueous slurry of potassium hydroxide and calcium hydroxide to said tubular reactor at a reaction temperature of 70 ℃ to 100 ℃ and a pressure sufficient to maintain perfluorobutanesulfonyl fluoride in a liquid state;
(iii) drying the reaction mixture to obtain a solid containing calcium fluoride and potassium perfluorobutane sulfonate;
(iv) dissolving the solid with ethanol at 65-76 deg.C; and
(v) crystallizing the dissolved ethanol solution containing the potassium perfluorobutane sulfonate to obtain the potassium perfluorobutane sulfonate.
2. The process of claim 1 wherein the continuous addition of the aqueous slurry of perfluorobutanesulfonyl fluoride and potassium hydroxide and calcium hydroxide to the tubular reactor results in a ratio of perfluorobutanesulfonyl fluoride: potassium hydroxide: calcium hydroxide: controlling the molar ratio of water to be 1: 1-1.1:0.5-0.55: 7-60.
3. The process of claim 1 wherein the continuous addition of the aqueous slurry of perfluorobutanesulfonyl fluoride and potassium hydroxide and calcium hydroxide to the tubular reactor results in a ratio of perfluorobutanesulfonyl fluoride: potassium hydroxide: calcium hydroxide: controlling the molar ratio of water to be 1: 1-1.08:0.5-0.54: 8-50.
4. The process of claim 1 wherein the continuous addition of the aqueous slurry of perfluorobutanesulfonyl fluoride and potassium hydroxide and calcium hydroxide to the tubular reactor results in a ratio of perfluorobutanesulfonyl fluoride: potassium hydroxide: calcium hydroxide: controlling the molar ratio of water to be 1: 1-1.05:0.5-0.52: 10-40.
5. The process according to any one of claims 1 to 4, wherein the reaction temperature is from 80 to 95 ℃.
6. The process according to any one of claims 1 to 4, wherein the reaction temperature is from 85 to 90 ℃.
7. The process according to any one of claims 1 to 4, wherein the reaction temperature is from 86 to 88 ℃.
8. The process according to any one of claims 1 to 4, characterized in that the pressure of the tubular reactor is between 0.10 and 0.80 MPa.
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