CN104610221A - Preparation method of 1-propenyl-1,3-sultone - Google Patents
Preparation method of 1-propenyl-1,3-sultone Download PDFInfo
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- CN104610221A CN104610221A CN201510026243.7A CN201510026243A CN104610221A CN 104610221 A CN104610221 A CN 104610221A CN 201510026243 A CN201510026243 A CN 201510026243A CN 104610221 A CN104610221 A CN 104610221A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
- C07D327/04—Five-membered rings
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Abstract
The invention relates to a preparation method of 1-propenyl-1,3-sultone. The method comprises the following steps: propargyl alcohol and pre-treated anion exchange resin are added to an aqueous solution of hydrosulphite, air is introduced, the mixture is heated and stirred, and heat preservation reaction is performed, and a mixed solution is obtained; the obtained mixed solution is cooled and filtered to obtain filtrate and a filter cake; a chromatographic column is filled with the filter cake and leached with protonic acid, leacheate is collected and distilled to obtain a brown and thick liquid; the obtained brown and thick liquid is cooled to the room temperature and subjected to decompression dehydration to obtain 1-propenyl-1,3-sultone. The preparation method provides possibility for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of 1-propenyl-1,3-sulfonic acid lactone, belong to organic compound preparation technical field.
Background technology
1-propenyl-1,3-sultones is lithium-ion battery electrolytes additive, it is degradation property additive, Main Function forms SEI (solid elec-trolyte interface) layer at graphite electrode surface, to avoid lithium to embed the battery performance rapid attenuation caused, improve battery performance.
Have benefited from the fast development of field of lithium ion battery and the huge market space thereof, 1-propenyl-1,3-sulfonic acid lactone is as one additive of good performance, and its synthetic method obtains to be studied widely.But because yield is low, the more high reason of complex process, cost, fail to realize large-scale industrial production all the time.Existing 1-propenyl-1, the synthesis technique of 3-sultones is: take propiolic alcohol as raw material, adopt the synthetic route of addition, acidifying, dehydration condensation, domestic have two sections to synthesize patent: CN101456856A and CN101659653A, all adopt said synthesis route, all adopt propiolic alcohol and sulphite or hydrosulphite to carry out addition reaction in addition step, due to the easy polymerization reaction take place of this step cause the finished product yield and purity lower.
Summary of the invention
In view of problems such as yield in prior art are low, purity is low, the invention provides a kind of 1-propenyl-1, the preparation method of 3-sultones, anionite-exchange resin is added in addition step, ion-exchange is carried out with reaction product, thus effectively solve the problems referred to above, there is the advantages such as product yield is high, purity is high, preparation method is simple, be widely used, for suitability for industrialized production provides possibility.
The technical scheme that the present invention solves the problems of the technologies described above is as follows:
A preparation method for 1-propenyl-1,3-sulfonic acid lactone, comprises the following steps:
1) in the aqueous solution of hydrosulphite, add propiolic alcohol, through pretreated anionite-exchange resin, pass into air, heated and stirred, keep temperature to react, obtain mixed solution;
2) by step 1) mixed solution that obtains, cooling is filtered, and obtains filtrate and filter cake; Described filter cake is loaded in chromatography column, uses protonic acid drip washing, collect leacheate, distill, obtain brown viscous liquid;
3) by step 2) in the brown viscous liquid that obtains be down to room temperature, decompression dehydration, obtain 1-propenyl-1,3-sulfonic acid lactone.
There is following reaction scheme:
Further, step 1) in, described hydrosulphite is sodium bisulfite or Potassium hydrogen sulfite; The massfraction of described sodium sulfite solution sulfite hydrogen sodium is 20%, and the massfraction of described bisulfite potassium solution sulfite hydrogen potassium is 22%; The mol ratio of described propiolic alcohol and hydrosulphite is 2: 1 to 4: 1, and described hydrosulphite is 1: 4 to 1: 6 with the mass ratio through pretreated anionite-exchange resin; Described anionite-exchange resin model is 201 × 7, in D201,717 any one.
Further, the pretreatment process of described anionite-exchange resin is: wash described anionite-exchange resin to aqueous phase achromaticity and clarification, be soaked in water 24h, 2h is soaked again with the hydrochloric acid soln of massfraction 2%, be washed to pH=4, soak 2h with the sodium hydroxide solution of massfraction 5%, being washed to pH is 8-9.
Further, step 1) reaction conditions be: pass into air bubbling with 300-500mL/min, utilize oil bath to heat, be warming up to interior temperature 85-90 DEG C, insulation reaction 4h, the mixed solution obtained can not make fuchsin solution fade.
Further, step 2) in, described protonic acid is sulfuric acid, and the massfraction of described sulfuric acid is 30%-35%, and the mol ratio of described sulfuric acid and hydrosulphite is 1: 1; Step 2) in, by step 1) cooling of the mixed solution that obtains makes its temperature lower than 50 DEG C, and distillation condition is temperature is 75-80 DEG C, pressure is 0.09MPa.
Further, step 3) in, described decompression dehydration condition is: pressure is 300Pa, and temperature is 90-130 DEG C.
The total recovery 60%-65% of the 1-propenyl-1,3-sulfonic acid lactone utilizing aforesaid method to obtain, purity is greater than 99.9%, and fusing point is 82-83 DEG C.
The invention has the beneficial effects as follows:
The method that the present invention have employed ion-exchange uniquely simplifies operating process, improves reaction yield simultaneously, reduces raw materials cost, produces provide possibility for large-scale industrial.The present invention take propiolic alcohol as raw material, and obtain compound 1-propenyl-1,3-sulfonic acid lactone, total recovery 60%-65% through sulfonation reaction, ion-exchange, acidification reaction, dehydration reaction, purity is greater than 99.9%, fusing point 82-83 DEG C.
At present, 1-propenyl-1, the preparation of 3-sultones generally adopts the synthetic route of addition, acidifying, dehydration condensation, all adopt propiolic alcohol and sulphite or hydrosulphite to carry out addition reaction in addition step, because when addition reaction, product is easily polymerized and causes product yield and purity lower.
Usually, ion exchange resin is mainly used in the isolation andpurification of product, does not have relevant report in the preparation method of 1-propenyl-1,3-sulfonic acid lactone.The present invention adopts ion exchange method to prepare 1-propenyl-1, the anionite-exchange resin that the present invention of 3-sultones selects has special selectivity to the sulfonate in reaction system of the present invention, if the effect adopting other ion exchange resin can not reach same, even successfully target product can not be prepared, the reaction mechanism that the present invention adopts ion exchange method to prepare 1-propenyl-1,3-sulfonic acid lactone is:
In addition, the present invention also have selected the absorption parameter that best experiment condition determines suitable ion exchange resin, prepared by the present invention 1-propenyl-1,3-sulfonic acid lactone total recovery reaches 60%-65%, purity is greater than 99.9%, far away higher than the product yield in currently available technology and purity.
Embodiment
Be described principle of the present invention and feature below, example, only for explaining the present invention, is not intended to limit scope of the present invention.
A preparation method for 1-propenyl-1,3-sulfonic acid lactone, comprises the following steps:
1) pre-treatment is carried out to anionite-exchange resin: wash described anionite-exchange resin to aqueous phase achromaticity and clarification, be soaked in water 24h, then soak 2h with the hydrochloric acid soln of massfraction 2%, is washed to pH=4, soak 2h with the sodium hydroxide solution of massfraction 5%, being washed to pH is 8-9.
2) in the aqueous solution of massfraction 20% sodium bisulfite or the aqueous solution of massfraction 22% Potassium hydrogen sulfite, add propiolic alcohol, through pretreated anionite-exchange resin, (model is 201 × 7, D201 or 717), the mol ratio of described propiolic alcohol and hydrosulphite is 2: 1 to 4: 1, described hydrosulphite is 1: 4 to 1: 6 with the mass ratio through pretreated anionite-exchange resin, air bubbling is passed into 300-500mL/min, oil bath is utilized to heat, stir simultaneously, be warming up to interior temperature 85-90 DEG C and start timing insulation, insulation reaction 4h, obtain mixed solution, get 1mL mixed solution, dripping 1 massfraction is the fuchsin solution of 1%, fuchsin solution is colour-fast,
3) by step 1) mixed solution that obtains, be cooled to lower than 50 DEG C, filter, obtain filtrate and filter cake; Described filter cake is loaded in chromatography column, with the dilute sulphuric acid drip washing of massfraction 30%-35%, the mol ratio of described dilute sulphuric acid and sodium bisulfite or Potassium hydrogen sulfite is 1: 1, collects leacheate, temperature 75-80 DEG C, pressure is underpressure distillation under 0.09MPa condition, obtains brown viscous liquid;
4) by step 2) in the brown viscous liquid that obtains be down to room temperature, assembling oil pump dewatering unit, pressure be 300Pa, temperature be 90-130 DEG C of condition under decompression dehydration, underpressure distillation obtains white solid, is 1-propenyl-1,3-sulfonic acid lactone, described 1-propenyl-1, the total recovery 60%-65% of 3-sultones, purity is greater than 99.9%, fusing point 82-83 DEG C.
Embodiment 1
Pre-treatment is carried out to anionite-exchange resin: washing anionite-exchange resin (model is 201 × 7) is to aqueous phase achromaticity and clarification, be soaked in water 24h, use the HCl solution soaking 2h of massfraction 2% again, be washed to pH=4, soak 2h with the sodium hydroxide solution of massfraction 5% again, being washed to pH is 8;
41.6g sodium bisulfite (0.4mol) is dropped into successively in 500mL there-necked flask, tap water 166.5g (9.24mol), stir entirely molten, continue again to add 44.8g propiolic alcohol (0.8mol), the anionite-exchange resin of the above-mentioned process of 166.4g, air bubbling is passed into 300mL/min, oil bath heated and stirred, reaction system is colourless transparent liquid, be warming up to interior temperature 85 DEG C of systems and start timing insulation, system does not have obvious heat release and rushes warm phenomenon, insulation 4h reaction is complete, obtain mixed solution, get 1mL mixed solution, dripping 1 massfraction is the fuchsin solution of 1%, fuchsin solution is colour-fast.
System is cooled to temperature to 49 DEG C, above-mentioned mixed solution is filtered, obtain filtrate and filter cake; Filter cake is loaded in chromatography column, with the above-mentioned chromatography column of dilute sulphuric acid drip washing of 261.3g massfraction 30%, collect leacheate; Leacheate being transferred to volume is in the single port bottle of 1L, and temperature is 75 DEG C, pressure is desolventizing under 0.09MPa reduced pressure, after desolventizing, obtains 50g brown viscous liquid.
Brown viscous liquid is cooled to room temperature, assembling oil pump dewatering unit is (by still head, air set pipe forms), pressure is 300Pa, temperature is utilize oil pump to dewater under 90 DEG C of conditions, distill to obtain white solid 31.2g, be 1-propenyl-1, 3-sultones, yield is 65% (the calculating employing following methods of yield: sodium bisulfite reacts completely, product theoretical yield is 0.4mol, i.e. 48.0g, therefore yield is 31.2g/48g=65%, embodiment 2 and embodiment 3 also adopt the calculated yield that uses the same method), the purity that GC detects is 99.96%, fusing point is 82 DEG C.
Embodiment 2
Pre-treatment is carried out to anionite-exchange resin: washing anionite-exchange resin (model is D201) is to aqueous phase achromaticity and clarification, be soaked in water 24h, use the HCl solution soaking 2h of massfraction 2% again, be washed to pH=4, soaking 2h with the sodium hydroxide solution of massfraction 5%, being washed to pH is 9.
48.1g Potassium hydrogen sulfite (0.4mol) is dropped into successively in 500mL there-necked flask, tap water 166.5g (9.24mol), stir until all dissolve, 89.6g propiolic alcohol (1.6mol) is added in solution, 288.6g anionite-exchange resin, air bubbling is passed into 500mL/min, oil bath heated and stirred, reaction system is colourless transparent liquid, be warming up to interior temperature 90 DEG C of systems and start timing insulation, system does not have obvious heat release and rushes warm phenomenon, insulation 4h reaction is complete, obtain mixed solution, get 1mL mixed solution, dripping 1 massfraction is the fuchsin solution of 1%, fuchsin solution is colour-fast.
System is cooled to temperature 30 DEG C, above-mentioned mixed solution is filtered, obtain filtrate and filter cake; Filter cake is loaded in chromatography column, with the above-mentioned chromatography column of dilute sulphuric acid drip washing of 224.0g massfraction 35%, collect leacheate; Leacheate being transferred to volume is in the single port bottle of 1L, and temperature is 80 DEG C, pressure is desolventizing under 0.09MPa reduced pressure, after desolventizing, obtains 55g brown viscous liquid.
Brown viscous liquid is cooled to room temperature, assembling oil pump dewatering unit (being made up of still head, air set pipe), pressure is 300Pa, temperature is utilize oil pump to dewater under 130 DEG C of conditions, distills to obtain white solid 28.8g, is 1-propenyl-1,3-sultones, yield is 60%, GC detection purity is 99.97%, and fusing point is 83 DEG C.
Embodiment 3
Pre-treatment is carried out to anionite-exchange resin: washing anionite-exchange resin (model is 717) is to aqueous phase achromaticity and clarification, be soaked in water 24h, use the HCl solution soaking 2h of massfraction 2% again, be washed to pH=4, soak 2h with the sodium hydroxide solution of massfraction 5% again, being washed to pH is 8.5;
41.6g sodium bisulfite (0.4mol) is dropped into successively in 500mL there-necked flask, tap water 166.5g (9.24mol), stir entirely molten, 67.2g propiolic alcohol (1.2mol) is added in above-mentioned solution, the anionite-exchange resin of the above-mentioned process of 208g, air bubbling is passed into 400mL/min, oil bath heated and stirred, reaction system is colourless transparent liquid, be warming up to interior temperature 87 DEG C of systems and start timing insulation, system does not have obvious heat release and rushes warm phenomenon, insulation 4h reaction is complete, obtain mixed solution, get 1mL mixed solution, dripping 1 massfraction is the fuchsin solution of 1%, fuchsin solution is colour-fast.
System is cooled to temperature to 20 DEG C, above-mentioned mixed solution is filtered, obtain filtrate and filter cake; Filter cake is loaded in chromatography column, with the above-mentioned chromatography column of dilute sulphuric acid drip washing of 245.0g massfraction 32%, collect leacheate; Leacheate being transferred to volume is in the single port bottle of 1L, and temperature is 78 DEG C, pressure is desolventizing under 0.09MPa reduced pressure, after desolventizing, obtains 58g brown viscous liquid.
Brown viscous liquid is cooled to room temperature, assembling oil pump dewatering unit (being made up of still head, air set pipe), pressure is 300Pa, temperature is utilize oil pump to dewater under 110 DEG C of conditions, distill to obtain white solid 30.7g, be 1-propenyl-1,3-sulfonic acid lactone, yield is 64%, it is 99.99% that GC detects purity, and fusing point is 82.5 DEG C.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for 1-propenyl-1,3-sulfonic acid lactone, is characterized in that, comprises the following steps:
1) in the aqueous solution of hydrosulphite, add propiolic alcohol, through pretreated anionite-exchange resin, pass into air, heated and stirred, keep temperature to react, obtain mixed solution;
2) by step 1) filter after the cooling of the mixed solution that obtains, obtain filtrate and filter cake; Described filter cake is loaded in chromatography column, uses protonic acid drip washing, collect leacheate, distill, obtain brown viscous liquid;
3) by step 2) in the brown viscous liquid that obtains be down to room temperature, decompression dehydration, obtain 1-propenyl-1,3-sulfonic acid lactone.
2. the preparation method of a kind of 1-propenyl-1,3-sulfonic acid lactone according to claim 1, is characterized in that, step 1) in, described hydrosulphite is sodium bisulfite or Potassium hydrogen sulfite.
3. the preparation method of a kind of 1-propenyl-1,3-sulfonic acid lactone according to claim 1, is characterized in that, step 1) in, described anionite-exchange resin model is 201 × 7, in D201,717 any one.
4. the preparation method of a kind of 1-propenyl-1,3-sulfonic acid lactone according to claim 2, is characterized in that, step 1) in, the massfraction of described sodium sulfite solution sulfite hydrogen sodium is 20%; The massfraction of described bisulfite potassium solution sulfite hydrogen potassium is 22%.
5. a kind of 1-propenyl-1 according to claim 1, the preparation method of 3-sultones, it is characterized in that, step 1) in, the mol ratio of described propiolic alcohol and hydrosulphite is 2: 1 to 4: 1, and described hydrosulphite is 1: 4 to 1: 6 with the mass ratio through pretreated anionite-exchange resin.
6. the preparation method of a kind of 1-propenyl-1,3-sulfonic acid lactone according to claim 1, it is characterized in that, described protonic acid is sulfuric acid, and the massfraction of described sulfuric acid is 30%-35%, and the mol ratio of described sulfuric acid and hydrosulphite is 1: 1.
7. a kind of 1-propenyl-1 according to any one of claim 1 to 6, the preparation method of 3-sultones, it is characterized in that, step 1) in, the pretreatment process of described anionite-exchange resin is: wash described anionite-exchange resin to aqueous phase achromaticity and clarification, be soaked in water 24h, 2h is soaked again with the hydrochloric acid soln of massfraction 2%, be washed to pH=4, soak 2h with the sodium hydroxide solution of massfraction 5%, being washed to pH is 8-9.
8. a kind of preparation method of 1-propenyl-1,3-sulfonic acid lactone according to any one of claim 1 to 6, is characterized in that, step 1) in, the described speed passing into air is 300-500mL/min, and the temperature of described heating is 85-90 DEG C, and the time of described reaction is 4h.
9. a kind of preparation method of 1-propenyl-1,3-sulfonic acid lactone according to any one of claim 1 to 6, is characterized in that, step 2) in, described distillation condition is temperature is 75-80 DEG C, pressure is 0.09MPa.
10. a kind of preparation method of 1-propenyl-1,3-sulfonic acid lactone according to any one of claim 1 to 6, is characterized in that, step 3) in, described decompression dehydration condition is: temperature is 90-130 DEG C, and pressure is 300Pa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107857752A (en) * | 2017-11-27 | 2018-03-30 | 九江天赐高新材料有限公司 | A kind of preparation method of the sultones of acrylic 1,3 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107857752A (en) * | 2017-11-27 | 2018-03-30 | 九江天赐高新材料有限公司 | A kind of preparation method of the sultones of acrylic 1,3 |
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