CN101747237A - Method for preparing methanesulfonyl fluoride CH3SO2F by methylsufonyl chloride CH3SO2Cl - Google Patents

Method for preparing methanesulfonyl fluoride CH3SO2F by methylsufonyl chloride CH3SO2Cl Download PDF

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Publication number
CN101747237A
CN101747237A CN200810243623A CN200810243623A CN101747237A CN 101747237 A CN101747237 A CN 101747237A CN 200810243623 A CN200810243623 A CN 200810243623A CN 200810243623 A CN200810243623 A CN 200810243623A CN 101747237 A CN101747237 A CN 101747237A
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methanesulfonyl
fluoride
reaction
chloride
ch3so2cl
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陶荣辉
许文林
许坚
王雅琼
徐晓强
沙红霞
舒亚飞
司宗飞
蒋德生
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Yangzhou University
Zhangjiagang Guotai Huarong New Chemical Materials Co Ltd
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Yangzhou University
Zhangjiagang Guotai Huarong New Chemical Materials Co Ltd
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Abstract

The invention discloses a method for preparing methanesulfonyl fluoride CH3SO2F by methylsufonyl chloride CH3SO2Cl, the methylsufonyl chloride CH3SO2Cl is used as raw material, and the steps of the method are as follows: in the reacting device, water H2O, potassium fluoride KF and methylsufonyl chloride CH3SO2Cl are mixed, or the water solution of potassium fluoride KF and the methylsufonyl chloride CH3SO2Cl are mixed, and then the fluorinated reaction occurs, and the product methanesulfonyl fluoride CH3SO2F and the subsidiary product potassium fluoride KF are obtained. The advantages of the invention are as follows: the reaction speed is fast, the reaction time is short, the hydrolysis capacity of the methylsufonyl chloride CH3SO2Cl and the methanesulfonyl fluoride CH3SO2F is small, the selectivity and the yield coefficient of the product are increased, and the invention provides very favorable conditions for separation and purification of the reaction product, meanwhile, the invention is beneficial for realizing the clean production of the process, and greatly reduces the preparation cost, and is beneficial for realizing the large-scale industrialization.

Description

Methanesulfonyl chloride CH 3SO 2Cl prepares methanesulfonyl fluoride CH 3SO 2The method of F
Technical field
The present invention relates to a kind of preparation methanesulfonyl fluoride CH 3SO 2The method of F, particularly a kind of Methanesulfonyl chloride CH 3SO 2Cl prepares methanesulfonyl fluoride CH 3SO 2The method of F belongs to field of fine chemical.
Background technology
Methanesulfonyl fluoride CH 3SO 2F is the important foundation raw material of the novel Chemicals of complex functionality type in the field of fine chemical, mainly as fine chemistry industry synthetic raw material and analytical reagent, also synthesizes the raw material of trifluoromethyl sulfonic acid fluoride as electrochemical production.
Methanesulfonyl fluoride, molecular formula are CH 3SO 2F, molecular weight are 98.10, and colourless or little yellow liquid, boiling point are 123-124 ℃, and relative density (water=1.0) is 1.35, and saturation vapour pressure (80 ℃) is 5.31kPa, and is water insoluble, is dissolved in ethanol, ether and the anhydrous hydrogen fluoride.Methanesulfonyl fluoride stable in properties, flammable, tool severe corrosive, strong and stimulating can cause that human body is burnt, severe toxicity, are subjected to the deleterious corrosive gases hydrogen fluoride of pyrolytic decomposition generation.
Methanesulfonyl chloride, molecular formula are CH 3SO 2Cl, molecular weight is 114.55, colourless or little yellow liquid, fusing point are-32 ℃, and boiling point is 164 ℃, relative density (water=1.0) is 1.48, relative vapour density (air=1.0) is 3.9, and saturation vapour pressure is (53 ℃) 1.60kPa, and flash-point is 110 ℃, water insoluble, be dissolved in ethanol, ether and the anhydrous hydrogen fluoride.Methanesulfonyl chloride stable in properties, flammable, hypertoxic, tool severe corrosive, strong and stimulating can cause human body and burn, and are subjected to the deleterious corrosive gases hydrogenchloride of pyrolytic decomposition generation.
Potassium monofluoride, molecular formula are KF, and molecular weight is 58.1, colourless cube of crystallization, and easy deliquescence, fusing point is 858 ℃, and boiling point is 1505 ℃, and relative density (water=1) is 2.48, does not fire, and extremely water-soluble, hydrofluoric acid, liquefied ammonia are insoluble to alcohol.Under 18 ℃, can dissolve the 92.3g Potassium monofluoride in the 100g water.The Potassium monofluoride stable in properties, contact acid or acid gas can produce toxic gas hydrogen fluoride.Form agent as analytical reagent, complex compound, and be used for glass-engraving and food is anticorrosion, also as sterilant, fluorizating agent etc.
The corrodibility of hydrogen fluoride gas and anhydrous hydrofluoric acid is all very strong, and most acid are had hydrofluoric acid resistants not of good corrosion resistant tantalum, titanium, zirconium, and stainless steel is hydrofluoric acid resistant not also.All siliceous materials all can not because silicon very easily reacts with hydrofluoric acid, produce SiF as the anticorrosive material of hydrofluoric acid 4Gas.Gold, platinum and silver all have superior corrosion resistance to hydrofluoric acid aqueous solution and anhydrous hydrogen fluoride.Copper, nickel and alloy be hydrofluoric acid resistant and hydrogen fluoride gas all.Polyethylene, polypropylene, polyvinyl chloride, polystyrene, phenolic aldehyde, epoxy etc. all have suitable erosion resistance, penton and the higher temperature of tetrafluoroethylene ability to the diluted acid of normal temperature in the plastics.
The corrodibility of HCl gas and hydrochloric acid is also very strong, the standard potential of most of metals is all under the hydrogen standard potential, so material is when existing hydrionic hydrochloric acid soln to contact, metal ion corrosion rapidly enters solution with ionic condition, hydrogen ion is reduced with gas and emits, have only some precious metals, corrosion-resistant as tantalum, platinum, gold and silver etc. to hydrochloric acid.Carry pipeline, valve, pump and the gas blower of hydrochloric acid soln and hydrogen chloride gas can use impermeable graphite, phenolic aldehyde, polyvinyl chloride or making such as other plastics, vulcanite, also available rubber and plastic-lined pipeline or steel systeming equipment.The storage of a large amount of hydrochloric acid and transportation are mainly with rubber lined storage tank and tank car.
If it is contain HCl gas or hydrochloric acid in HF gas and the hydrofluoric acid, extremely difficult especially to the selection of equipment, pipe material.So in the organic synthesis process, can be earlier with CH 3SO 2Chlorine among the Cl is replaced by fluorine, promptly synthetic CH 3SO 2F avoids and improves this situation.
With CH 3SO 2Cl is the synthetic CH of feedstock production 3SO 2The method of F mainly contains two kinds at present, and first kind is CH 3SO 2Cl and HF reaction, second kind is CH 3SO 2Cl and KFHF reaction, chemical equation is respectively:
CH 3SO 2Cl+HF→CH 3SO 3F+HCl
CH 3SO 2Cl+KF·FH→CH 3SO 3F+KCl+HF
Above-mentioned these two kinds with CH 3SO 2Cl is the synthetic CH of feedstock production 3SO 2The major defect of F method is: all used HF in reaction process, this has brought very big difficulty for the Material Selection of equipment, pipeline and the separation and purification of product, and degree of purity of production is low, and carries out causing CH easily in the reaction process in the HF aqueous solution 3SO 2Cl and CH 3SO 2The generation of the hydrolysis reaction of F makes product C H 3SO 2The selectivity of F and yield reduce.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide that a kind of preparation method is simple, preparation cost is low, equipment material selects easily, is beneficial to the product separation and purification, uses Methanesulfonyl chloride CH 3SO 2Cl and Potassium monofluoride KF prepared in reaction methanesulfonyl fluoride CH 3SO 2The method of F.
The technical scheme that realizes above-mentioned purpose is: a kind of Methanesulfonyl chloride CH 3SO 2Cl prepares methanesulfonyl fluoride CH 3SO 2The method of F is with Methanesulfonyl chloride CH 3SO 2Cl is a raw material, and described method steps is as follows:
In conversion unit, with water H 2O, Potassium monofluoride KF and Methanesulfonyl chloride CH 3SO 2Cl mixes, or with the Potassium monofluoride KF aqueous solution and Methanesulfonyl chloride CH 3SO 2Cl mixes, and fluoro-reaction takes place, and obtains product methanesulfonyl fluoride CH 3SO 2F and by product potassium chloride (KCl).
Further, the material Methanesulfonyl chloride CH that uses in the fluoro-reaction 3SO 2The mol ratio of Cl and Potassium monofluoride KF is 1.0: 1.2～3.2, and temperature of reaction is 10 ℃～60 ℃.
Further, the Potassium monofluoride KF aqueous solution volumetric molar concentration of using in the fluoro-reaction is 4.0mol/L～19.4mol/L.
Further, described conversion unit is that the still formula stirs any one in chemical reactor, tubular chemical reactor or the static mixer.
Chemical equation of the present invention is:
CH 3SO 2Cl+KF→CH 3SO 2F+KCl
Realize that the main technique equipment that the present invention needs is: the still formula stirs chemical reaction equipments such as chemical reactor, tubular chemical reactor or static mixer.
Adopt the benefit of technique scheme to be: the present invention adopts Methanesulfonyl chloride CH 3SO 2Cl and Potassium monofluoride KF reactant aqueous solution prepare methanesulfonyl fluoride CH 3SO 2F, or Methanesulfonyl chloride CH 3SO 2Cl and Potassium monofluoride KF and water H 2O prepared in reaction methanesulfonyl fluoride CH 3SO 2The processing method of F, the present invention changes traditional preparation method at present, has used Potassium monofluoride KF in reaction process, and has avoided using hydrogen fluoride HF, this has brought very big convenience for the Material Selection of equipment, pipeline and the separation and purification of product, the preparation method is simple, alleviates the difficulty that lectotype selection and material are selected simultaneously greatly, and is not high to equipment requirements, preparation cost is low, speed of response is fast, and the reaction times is short, Methanesulfonyl chloride CH 3SO 2Cl and methanesulfonyl fluoride CH 3SO 2The amount of hydrolysis of F is few, product selectivity and yield height, and, help the cleaner production of implementation procedure for the separation and purification of reaction product provides very favorable condition, and reduced preparation cost significantly, be convenient to realize heavy industrialization.
Description of drawings
Accompanying drawing is a process flow sheet of the present invention.
Embodiment
The present invention is further detailed explanation below in conjunction with drawings and Examples.
Embodiment one
Main technique equipment stirs chemical reactor for the still formula.
As shown in the figure, a kind of Methanesulfonyl chloride CH 3SO 2Cl prepares methanesulfonyl fluoride CH 3SO 2The method of F, described processing step is as follows:
With 1125.0g Potassium monofluoride KF and 2000ml water H 2O adds the 3000ml still formula that is provided with whipping appts and heat-exchanger rig and stirs in the chemical reactor, drips 1851.9g Methanesulfonyl chloride CH under agitation condition and heat transfer boundary condition 3SO 2Cl moves hot speed and CH by control 3SO 2The rate of addition of Cl, fluoro-reaction takes place, CH in 10 ℃～60 ℃ of controlled temperature 3SO 2After Cl dropwises, continue to keep 15min of following reaction times of whipped state, obtain thick product methanesulfonyl fluoride CH 3SO 2F and by product potassium chloride (KCl), reacting rear material are measured through gas chromatographic analysis and are obtained Methanesulfonyl chloride CH 3SO 2The reaction conversion ratio of Cl 〉=90%, methanesulfonyl fluoride CH 3SO 2The molar yield of F 〉=85%.
Embodiment two
Main technique equipment is tubular chemical reactor.
As shown in the figure, a kind of Methanesulfonyl chloride CH 3SO 2Cl prepares methanesulfonyl fluoride CH 3SO 2The method of F, described processing step is as follows:
At room temperature, with the aqueous solution of 12.4mol/L Potassium monofluoride KF with 1000ml and 6.0mol Methanesulfonyl chloride CH 3SO 2The ratio of Cl enters tubular chemical reactor, and the operation absolute pressure is 0.5MPa, and fluoro-reaction takes place 20 ℃～40 ℃ of the temperature in the control tubular chemical reactor, obtains thick product methanesulfonyl fluoride CH 3SO 2F and by product potassium chloride (KCl), reacting rear material are measured through gas chromatographic analysis and are obtained: Methanesulfonyl chloride CH 3SO 2The reaction conversion ratio of Cl 〉=90%, methanesulfonyl fluoride CH 3SO 2The molar yield of F 〉=92%.
Embodiment three
Main technique equipment is: major equipment is a static mixer.
As shown in the figure, a kind of Methanesulfonyl chloride CH 3SO 2Cl prepares methanesulfonyl fluoride CH 3SO 2The method of F, described processing step is as follows:
At room temperature, with the aqueous solution of 19.4mol/L Potassium monofluoride KF with 2000ml and 6.1mol Methanesulfonyl chloride CH 3SO 2The ratio of Cl enters static mixer, and the operation absolute pressure is 1.0MPa, under the adiabatic condition fluoro-reaction takes place, and 50 ℃～60 ℃ of the temperature outs of reaction mass obtain product methanesulfonyl fluoride CH 3SO 2F and by product potassium chloride (KCl).Reacting rear material is measured through gas chromatographic analysis and is obtained: Methanesulfonyl chloride CH 3SO 2The reaction conversion ratio of Cl 〉=99%, methanesulfonyl fluoride CH 3SO 2The molar yield of F 〉=96%.
Embodiment four
Main technique equipment stirs chemical reactor for the still formula.
As shown in the figure, a kind of Methanesulfonyl chloride CH 3SO 2Cl prepares methanesulfonyl fluoride CH 3SO 2The method of F, described processing step is as follows:
Stir in the chemical reactor 19.4mol/L the aqueous solution 1000ml of Potassium monofluoride KF adds the 3000ml still formula that is provided with whipping appts and heat-exchanger rig, under agitation condition and heat transfer boundary condition, drip 6.1mol Methanesulfonyl chloride CH 3SO 2Cl moves hot speed and CH by control 3SO 2The rate of addition of Cl, fluoro-reaction takes place, CH in 10 ℃～30 ℃ of controlled temperature 3SO 2After Cl dropwises, continue to keep 20min of following reaction times of whipped state, obtain thick product methanesulfonyl fluoride CH 3SO 2F has the crystallization of by product potassium chloride (KCl) to separate out simultaneously.Reacting rear material is measured through gas chromatographic analysis and is obtained Methanesulfonyl chloride CH 3SO 2The reaction conversion ratio of Cl 〉=85%, methanesulfonyl fluoride CH 3SO 2The molar yield of F 〉=80%.
Embodiment five
Main technique equipment is tubular chemical reactor.
As shown in the figure, a kind of Methanesulfonyl chloride CH 3SO 2Cl prepares methanesulfonyl fluoride CH 3SO 2The method of F, described processing step is as follows:
At room temperature, with the aqueous solution of 4.0mol/L Potassium monofluoride KF with 1000ml and 3.3mol Methanesulfonyl chloride CH 3SO 2The ratio of Cl enters tubular chemical reactor, and the operation absolute pressure is 0.5MPa, and fluoro-reaction takes place 10 ℃～20 ℃ of the temperature in the control tubular chemical reactor, obtains thick product methanesulfonyl fluoride CH 3SO 2F and by product potassium chloride (KCl), reacting rear material are measured through gas chromatographic analysis and are obtained: Methanesulfonyl chloride CH 3SO 2The reaction conversion ratio of Cl 〉=90%, methanesulfonyl fluoride CH 3SO 2The molar yield of F 〉=92%.
Remove the various embodiments described above, embodiment of the present invention also have a lot, and the technical scheme that all employings are equal to or equivalence is replaced is all within protection scope of the present invention.

Claims (4)

1. Methanesulfonyl chloride CH 3SO 2Cl prepares methanesulfonyl fluoride CH 3SO 2The method of F is with Methanesulfonyl chloride CH 3SO 2Cl is a raw material, it is characterized in that described method steps is as follows:
In conversion unit, with water H 2O, Potassium monofluoride KF and Methanesulfonyl chloride CH 3SO 2Cl mixes, or with the Potassium monofluoride KF aqueous solution and Methanesulfonyl chloride CH 3SO 2Cl mixes, and fluoro-reaction takes place, and obtains product methanesulfonyl fluoride CH 3SO 2F and by product potassium chloride (KCl).
2. Methanesulfonyl chloride CH according to claim 1 3SO 2Cl prepares methanesulfonyl fluoride CH 3SO 2The method of F is characterized in that: the material Methanesulfonyl chloride CH that uses in the fluoro-reaction 3SO 2The mol ratio of Cl and Potassium monofluoride KF is 1.0: 1.2～3.2, and temperature of reaction is 10 ℃～60 ℃.
3. Methanesulfonyl chloride CH according to claim 1 3SO 2Cl prepares methanesulfonyl fluoride CH 3SO 2The method of F is characterized in that: the Potassium monofluoride KF aqueous solution volumetric molar concentration of using in the fluoro-reaction is 4.0mol/L～19.4mol/L.
4. Methanesulfonyl chloride CH according to claim 1 3SO 2Cl prepares methanesulfonyl fluoride CH 3SO 2The method of F is characterized in that: described conversion unit is that the still formula stirs any one in chemical reactor, tubular chemical reactor or the static mixer.
CN200810243623A 2008-12-11 2008-12-11 Method for preparing methanesulfonyl fluoride CH3SO2F by methylsufonyl chloride CH3SO2Cl Pending CN101747237A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103864022A (en) * 2012-12-13 2014-06-18 中化蓝天集团有限公司 Sulfuryl fluoride preparation method
CN105198683A (en) * 2015-09-24 2015-12-30 信阳师范学院 Preparation method of sulfuryl fluoride compound
CN105669501A (en) * 2016-02-25 2016-06-15 湖北恒新化工有限公司 Preparing method of 2-naphthalene sulfuryl fluoride
CN112661676A (en) * 2020-12-15 2021-04-16 中船重工（邯郸）派瑞特种气体有限公司 Method for preparing methanesulfonyl fluoride from methanesulfonyl chloride
CN112724047A (en) * 2020-12-15 2021-04-30 中船重工（邯郸）派瑞特种气体有限公司 Device and method for preparing trifluoromethanesulfonyl fluoride
CN112760672A (en) * 2020-12-15 2021-05-07 中船重工（邯郸）派瑞特种气体有限公司 Method for electrochemically preparing trifluoromethyl sulfonyl fluoride from methyl sulfonyl chloride

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103864022A (en) * 2012-12-13 2014-06-18 中化蓝天集团有限公司 Sulfuryl fluoride preparation method
CN103864022B (en) * 2012-12-13 2015-10-28 中化蓝天集团有限公司 A kind of method preparing sulfuryl fluoride
CN105198683A (en) * 2015-09-24 2015-12-30 信阳师范学院 Preparation method of sulfuryl fluoride compound
CN105669501A (en) * 2016-02-25 2016-06-15 湖北恒新化工有限公司 Preparing method of 2-naphthalene sulfuryl fluoride
CN112661676A (en) * 2020-12-15 2021-04-16 中船重工（邯郸）派瑞特种气体有限公司 Method for preparing methanesulfonyl fluoride from methanesulfonyl chloride
CN112724047A (en) * 2020-12-15 2021-04-30 中船重工（邯郸）派瑞特种气体有限公司 Device and method for preparing trifluoromethanesulfonyl fluoride
CN112760672A (en) * 2020-12-15 2021-05-07 中船重工（邯郸）派瑞特种气体有限公司 Method for electrochemically preparing trifluoromethyl sulfonyl fluoride from methyl sulfonyl chloride
CN112760672B (en) * 2020-12-15 2022-04-08 中船(邯郸)派瑞特种气体股份有限公司 Method for electrochemically preparing trifluoromethyl sulfonyl fluoride from methyl sulfonyl chloride
CN112661676B (en) * 2020-12-15 2022-11-25 中船(邯郸)派瑞特种气体股份有限公司 Method for preparing methanesulfonyl fluoride from methanesulfonyl chloride
CN112724047B (en) * 2020-12-15 2023-10-17 中船(邯郸)派瑞特种气体股份有限公司 Device and method for preparing trifluoro methanesulfonyl fluoride

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Application publication date: 20100623