CN110105326A - A kind of preparation method of 1,3- propane sultone - Google Patents
A kind of preparation method of 1,3- propane sultone Download PDFInfo
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- CN110105326A CN110105326A CN201910141327.3A CN201910141327A CN110105326A CN 110105326 A CN110105326 A CN 110105326A CN 201910141327 A CN201910141327 A CN 201910141327A CN 110105326 A CN110105326 A CN 110105326A
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- propane sultone
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- sodium sulfite
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- C—CHEMISTRY; METALLURGY
- 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 present invention relates to the preparation methods of one kind 1,3- propane sultone comprising following steps: S1. is using 3- chloropropyl alcohol and sodium sulfite as raw material, it takes water as a solvent, after being sufficiently mixed in reaction vessel, temperature is controlled at 25-120 DEG C, reacts 4-48h, then decompression dehydration is concentrated, concentrated hydrochloric acid acidification is added into concentrate again, then controls temperature and at 0-80 DEG C and stirs 1-24h, then filter, filtrate concentration, obtains the concentrate of the hydroxy-propanesulfonic acid containing 3-；S2. at 40-110 DEG C, vacuum distillation makes the 3- hydroxy-propanesulfonic acid dehydration closed-loop in concentrate, obtains the crude product of the propane sultone containing 1,3- control S1 concentrate temperature；S3. by the crude product of the propane sultone Han 1,3- made from S2 carry out rectification process to get.Have the beneficial effect that process route is short, the generation three wastes are few, and post-processing is simple, and total recovery is up to 90% or more, and the purity of product is up to 99.9% or more.
Description
Technical field
The invention belongs to the synthesis fields of medicine intermediate, and in particular to the preparation side of one kind 1,3- propane sultone
Method.
Background technique
1,3-propane sultone is a kind of important chemical intermediate, it can and numerous species compound as mild as a dove
Under conditions of react, sulfonic acid group is accurately provided, thus assign the new performance of these compounds (as have hydrophily, resist it is quiet
The features such as electrically), be excellent universal sulfonating agent, and the important electroplating additive intermediate PPS, UPS of synthesis, DPS,
The critical materials of the products such as MPS, ZPS, POPS, SP.Functional form fine chemistry industry new material itself is also belonged to, medicine is widely used in
The industries such as chemical industry, photosensitive material, biochemistry, weaving, lubrication, wastewater treatment, surface treatment can also use lithium secondary battery
In, for enhancing circulating battery number and service life.
The method for preparing 1,3- propane sultone in the prior art has following several:
1) using allyl alcohol and sodium hydrogensulfite as raw material, it is sulfonated, acidification, dehydration, purification and etc. obtain target product.
Raw material allyl alcohol used in this method is toxic articles, larger to human body and environmental hazard, and acidization
Used in sulfuric acid can not eliminate, can be gradually concentrated during the dehydration process as the concentrated sulfuric acid, and then product is aoxidized, lead to by-product
More, product purity and yield be not high.
2) with 1,3- dihalopropane and sodium sulfite for raw material, sulfonated, acidification, esterification and etc. preparation target produce
Object.
This method needs larger using a large amount of organic solvent environmental pollution, while having in sulfonation process part original
Material reduces yield by secondary sulfonation.
3) using methacrylaldehyde and sodium hydrogensulfite as raw material, by addition, reduction, esterification, purification and etc. obtain target produce
Object.
The methacrylaldehyde that this method uses is oxidized easily, and needs hydrogenating reduction, the high requirements on the equipment, and production cost is opposite
It is higher.
There are also a series of methods for preparing target product by oxidation sulfinic acid ester etc..
But these method overall yields are not high, and by-product is more, and the high requirements on the equipment, are unfavorable for amplification life
It produces.
Further, since requirement of the lithium battery to material therefor is more harsh, purity of the market to 1,3- propane sultone
It is required that being also gradually increased, 1, the 3- propane sultone of conventional method preparation is increasingly difficult to meet the market demand.
Summary of the invention
The present invention provides the preparation method of one kind 1,3- propane sultone, it is intended to overcome the deficiencies of the prior art and provide
The new preparation method that a kind of process route is short, convenient post-treatment, yield are high, purity is good.
The technical scheme to solve the above technical problems is that the preparation method of one kind 1,3- propane sultone,
It includes the following steps:
S1. it using 3- chloropropyl alcohol and sodium sulfite as raw material, takes water as a solvent, after being sufficiently mixed in reaction vessel, control
Temperature reacts 4-48h at 25-120 DEG C, and then decompression dehydration is concentrated, then concentrated hydrochloric acid acidification is added into concentrate, then controls
Temperature is at 0-80 DEG C and stirs 1-24h, then filters, and filtrate concentration obtains the concentrate of the hydroxy-propanesulfonic acid containing 3-；
S2. control S1 concentrate temperature is at 40-110 DEG C, vacuum distillation, is dehydrated the 3- hydroxy-propanesulfonic acid in concentrate and closes
Ring obtains the crude product of the propane sultone containing 1,3-；
S3. by the crude product of the propane sultone Han 1,3- made from S2 carry out rectification process to get.
Based on the above technical solution, the present invention can also have following further specific choice or more preferably select.
Specifically, S1 sulfite sodium is reacting appearance with 3- chloropropyl alcohol again after being first configured to sodium sulfite solution with aqueous solvent
Mixing in device, the concentration of sodium sulfite solution are 10-30wt%.
Preferably, the molar ratio of 3- chloropropyl alcohol and sodium sulfite is 1:1.0-1.5 in S1.
Preferably, the molar ratio of HCl and 3- chloropropyl alcohol is 1-3:1 in the concentrated hydrochloric acid being added in S1.
Preferably, the concentration for the concentrated hydrochloric acid being added in S1 is 30-38wt%.
Preferably, for vacuum degree control when being evaporated under reduced pressure in S2 in -0.05MPa, the vacuum distillation duration is 2-4h.
Specifically, in S3 the step of rectification process are as follows: the crude product for obtaining S2 is put into rectifying column prior to 110-130 DEG C
Lower rectifying water removal after water removal, is warming up to 150-170 DEG C and carries out rectification process again, after to get.
Compared with prior art, the beneficial effects of the present invention are:
1. process route is short, without complicated post-processing, while total recovery is up to 90% or more, and the purity of products obtained therefrom
Up to 99.9% or more.
2. reaction carries out in aqueous solution, without using a large amount of organic solvent, and the material toxicity used is relatively also more
Low, compared with the prior art, technique used in the present invention is more environmentally-friendly.
3. easy to operate, equipment requirement is low, is suitble to industrialized production.
Detailed description of the invention
Fig. 1 is the gas chromatogram of 1,3- butane sultones made from the embodiment of the present invention 1；
Fig. 2 is the analysis result to Fig. 1 gas chromatogram.
Specific embodiment
Below in conjunction with drawings and the specific embodiments, the present invention is described in further detail, and example is served only for explaining
The present invention is not intended to limit the scope of the present invention.
Used method is the conventional method of this field, used drug unless otherwise noted in following embodiment
It is unless otherwise noted then commercial product.
Embodiment 1
The preparation method of one kind 1,3- propane sultone comprising following steps:
It S1. will be sufficiently mixed in the 3- chloropropyl alcohol of 1mol and sodium sulfite solution (concentration 10wt%) investment reaction vessel
It closes, the ratio between amount of substance of 3- chloropropyl alcohol and sodium sulfite is 1:1.5, controls temperature at 25 DEG C, 48h is reacted, then in vacuum
Decompression dehydration is concentrated at degree -0.08MPa and 90 DEG C.Then concentrated hydrochloric acid (concentration 30wt%) acidification is added into concentrate, adds
The ratio between amount of substance of HCl and 3- chloropropyl alcohol is 3:1 in the concentrated hydrochloric acid entered, and control temperature at 25 DEG C and stirs 12h, then mistake
Filter, filtrate concentration, obtains the concentrate containing 3- hydroxy-propanesulfonic acid；
S2., concentrate is evaporated under reduced pressure to (vacuum degree is -0.05MPa) at 40-110 DEG C closes the dehydration of 3- hydroxy-propanesulfonic acid
Ring (processing 2h), obtains the crude product of the propane sultone containing 1,3-；
S3. crude product S2 obtained is put into rectifying column prior to 120 DEG C or so rectifying water removals, after water removal, is warming up to
160 DEG C or so progress rectification process, obtaining 1, the 3- propane sultone of 0.91mol, (purity 99.93%, total recovery are
91%).
Embodiment 2
The preparation method of one kind 1,3- propane sultone comprising following steps:
It S1. will be sufficiently mixed in the 3- chloropropyl alcohol of 1mol and sodium sulfite solution (concentration 20wt%) investment reaction vessel
It closes, the ratio between amount of substance of 3- chloropropyl alcohol and sodium sulfite is 1:1.2, controls temperature at 90 DEG C, 12h is reacted, then in vacuum
Decompression dehydration is concentrated at degree -0.08MPa and 85 DEG C.Then concentrated hydrochloric acid (concentration 33.5wt%) acidification is added into concentrate,
The ratio between amount of substance of HCl and 3- chloropropyl alcohol is 2:1 in the concentrated hydrochloric acid of addition, and control temperature at 60 DEG C and stirs 8h, then mistake
Filter, filtrate concentration, obtains the concentrate containing 3- hydroxy-propanesulfonic acid；
S2., concentrate is evaporated under reduced pressure to (vacuum degree is -0.05MPa) at 40-110 DEG C closes the dehydration of 3- hydroxy-propanesulfonic acid
Ring (processing 2.5h), obtains the crude product of the propane sultone containing 1,3-；
S3. crude product S2 obtained is put into rectifying column prior to 120 DEG C or so rectifying water removals, after water removal, is warming up to
160 DEG C or so progress rectification process, obtaining 1, the 3- propane sultone of 0.93mol, (purity 99.90%, total recovery are
93%).
Embodiment 3
The preparation method of one kind 1,3- propane sultone comprising following steps:
It S1. will be sufficiently mixed in the 3- chloropropyl alcohol of 1mol and sodium sulfite solution (concentration 30wt%) investment reaction vessel
It closes, the ratio between amount of substance of 3- chloropropyl alcohol and sodium sulfite is 1:1.0, controls temperature at 120 DEG C, 4h is reacted, then in vacuum
Decompression dehydration is concentrated at degree -0.1MPa and 80 DEG C.Then concentrated hydrochloric acid (concentration 36wt%) acidification is added into concentrate, is added
Concentrated hydrochloric acid in the ratio between the amount of substance of HCl and 3- chloropropyl alcohol be 1:1, control temperature at 80 DEG C and stirs 2h, then filters, filters
Liquid concentration, obtains the concentrate containing 3- hydroxy-propanesulfonic acid；
S2., concentrate is evaporated under reduced pressure to (vacuum degree is -0.05MPa) at 40-110 DEG C closes the dehydration of 3- hydroxy-propanesulfonic acid
Ring (processing 4h), obtains the crude product of the propane sultone containing 1,3-；
S3. crude product S2 obtained is put into rectifying column prior to 120 DEG C or so rectifying water removals, after water removal, is warming up to
160 DEG C or so progress rectification process, obtaining 1, the 3- propane sultone of 0.90mol, (purity 99.95%, total recovery are
90%).
The target product prepared using embodiment 1 has obtained the gas chromatogram of target product as test sample, specific as schemed
Shown in 1,1, the 3- propane sultone purity of method preparation provided by the invention is up to 99.9% or more as shown in Figure 1.
By above embodiments as it can be seen that the preparation method of 1,3- propane sultone provided by the invention has process route
Short, convenient post-treatment, environmental pollution be small, high income and the advantages that good product purity.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. one kind 1, the preparation method of 3- propane sultone, which comprises the steps of:
S1. it using 3- chloropropyl alcohol and sodium sulfite as raw material, takes water as a solvent, after being sufficiently mixed in reaction vessel, controls temperature
At 25-120 DEG C, 4-48h is reacted, then decompression dehydration is concentrated, then concentrated hydrochloric acid acidification is added into concentrate, then controls temperature
At 0-80 DEG C and 1-24h is stirred, is then filtered, filtrate concentration obtains the concentrate of the hydroxy-propanesulfonic acid containing 3-；
S2. for control S1 concentrate temperature at 40-110 DEG C, vacuum distillation makes the 3- hydroxy-propanesulfonic acid dehydration closed-loop in concentrate,
The crude product of 1,3- propane sultone must be contained；
S3. by the crude product of the propane sultone Han 1,3- made from S2 carry out rectification process to get.
2. a kind of preparation method of 1,3- propane sultone according to claim 1, which is characterized in that S1 sulfite
Sodium first be configured to sodium sulfite solution with aqueous solvent after mixed in reaction vessel with 3- chloropropyl alcohol again, sodium sulfite solution it is dense
Degree is 10-30wt%.
3. a kind of preparation method of 1,3- propane sultone according to claim 1, which is characterized in that 3- chlorine third in S1
The molar ratio of alcohol and sodium sulfite is 1:1.0-1.5.
4. a kind of preparation method of 1,3- propane sultone according to claim 1, which is characterized in that be added in S1
The molar ratio of HCl and 3- chloropropyl alcohol is 1-3:1 in concentrated hydrochloric acid.
5. a kind of preparation method of 1,3- propane sultone according to claim 1, which is characterized in that be added in S1
The concentration of concentrated hydrochloric acid is 30-38wt%.
6. a kind of preparation method of 1,3- propane sultone according to claim 1, which is characterized in that depressurize and steam in S2
For vacuum degree control when evaporating in -0.05MPa, the vacuum distillation duration is 2-4h.
7. a kind of preparation method of 1,3- propane sultone according to any one of claims 1 to 6, which is characterized in that
The specific steps of rectification process in S3 are as follows: rectifying removes water at the crude product for obtaining S2 is put into rectifying column prior to 110-130 DEG C, removes
After water, be warming up to 150-170 DEG C and carry out rectification process again, after to get.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114805288A (en) * | 2021-01-20 | 2022-07-29 | 武汉松石科技股份有限公司 | Method for preparing 2, 4-butane sultone |
| CN115745948A (en) * | 2022-11-30 | 2023-03-07 | 广州理文科技有限公司 | Preparation method of 1, 3-propane sultone |
| CN115872973A (en) * | 2022-11-09 | 2023-03-31 | 贵州聚瑞新材料科技有限公司 | 5363 purification method of 1,3-propane sultone |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114805288A (en) * | 2021-01-20 | 2022-07-29 | 武汉松石科技股份有限公司 | Method for preparing 2, 4-butane sultone |
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| CN115872973A (en) * | 2022-11-09 | 2023-03-31 | 贵州聚瑞新材料科技有限公司 | 5363 purification method of 1,3-propane sultone |
| CN115745948A (en) * | 2022-11-30 | 2023-03-07 | 广州理文科技有限公司 | Preparation method of 1, 3-propane sultone |
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