CN108822075A - A kind of sulfuric acid vinyl ester synthesis technology - Google Patents
A kind of sulfuric acid vinyl ester synthesis technology Download PDFInfo
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- CN108822075A CN108822075A CN201810767082.0A CN201810767082A CN108822075A CN 108822075 A CN108822075 A CN 108822075A CN 201810767082 A CN201810767082 A CN 201810767082A CN 108822075 A CN108822075 A CN 108822075A
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- sulfuric acid
- vinyl ester
- acid vinyl
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
- C07D333/48—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom by oxygen atoms
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Abstract
The present invention relates to a kind of sulfuric acid vinyl ester synthesis technologies, include the following steps：Ethylene glycol reacts under the action of solvent and basic catalyst with chlorosulfuric acid；The molar ratio example of the ethylene glycol and chlorosulfuric acid is 1：0.8~2；The basic catalyst is organic amine, and catalyst and substrate ethylene glycol molar ratio are 1 ~ 4：1；The reaction temperature is at -40 ~ 50 DEG C；Filtering desalination obtains mother liquor after the reaction was completed, obtains crude product sulfuric acid vinyl ester after the mother liquor solvent evaporated；The crude product sulfuric acid vinyl ester obtains target product by refining purification.Compared with prior art, it is raw material that the invention patent, which is based on ethylene glycol and chlorosulfuric acid, and sulfuric acid vinyl ester is directly synthesized under base catalysis, and production process step is few, and easy to be easy to control, raw material is easy to get, and product only needs to recrystallize, and production cost is low, and the three wastes are few.
Description
Technical field
The invention belongs to technical field of fine, especially a kind of sulfuric acid vinyl ester synthesis technology.
Background technique
With the continuous expansion of lithium ion battery use scope, the technology of lithium ion battery is also being constantly progressive, lithium ion
Some additives are added in battery electrolyte, can substantially improve and improve the performance of battery.Sulfuric acid vinyl ester is called sulfuric acid Asia
Ethyl ester（Structure, which is seen below, to be shown）, it is a kind of excellent SEI film for additive, is able to suppress the decline of battery initial capacity, increases initial
Discharge capacity reduces the cell expansion after high temperature is placed, improves the charge-discharge performance and cycle-index of battery.
Sulfuric acid vinyl ester structural formula
From the point of view of the documents and materials of report, prepare sulfuric acid vinyl ester main method have it is following several：
（1）The direct addition of sulfur trioxide and ethylene oxide（See below formula）.It is molten in dioxane such as US3045627 patent report
Two kinds of raw materials directly react in agent, but ethylene oxide is excessively more；It is M that CN106831701A, which is reported in major catalyst,aObWith
NcOdMetal mixing oxide catalysis under, two kinds of raw materials directly react, and improve reaction of atomic economy, but due to raw material
The high toxicity and effumability of three oxygen part sulphur and ethylene oxide, pressure in production process is high, to production facility and safety to measure
It is more demanding.
（2）Ethylene sulfite is prepared with ethylene glycol and thionyl chloride reaction, then oxidative vinyl acetate obtains
To sulfuric acid vinyl ester（See below formula）, this is also the method for mainly producing the product at present.Such as CN102241662A,
CN106187989A etc. uses a large amount of water as solvent aoxidizing a step in the reaction process, and uses metallic catalyst（Such as sulphur
Sour iron, ruthenic chloride etc.）Therefore wastewater flow rate generates larger, not easy to handle.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above in the prior art and deficiencies, provide a kind of technique letter
The sulfuric acid vinyl ester synthesis technology single, production cost is low and three waste discharge is few.
The reaction equation of reaction involved in the present invention is as follows：
The present invention is achieved through the following technical solutions above-mentioned purpose：
A kind of sulfuric acid vinyl ester synthesis technology, includes the following steps：
（1）Ethylene glycol reacts under the action of solvent and basic catalyst with chlorosulfuric acid；The throwing of the ethylene glycol and chlorosulfuric acid
Expect that molar ratio is 1：0.8~2；The basic catalyst is organic amine, and catalyst and substrate ethylene glycol molar ratio are 1 ~ 4：1；
The reaction temperature is at -40 ~ 50 DEG C；
（2）Filtering desalination obtains mother liquor after the reaction was completed, obtains crude product sulfuric acid vinyl ester after the mother liquor solvent evaporated；
（3）The crude product sulfuric acid vinyl ester obtains target product by refining purification.
Further, the organic amine is tertiary amine；Still further preferably, the organic amine be triethylamine, tri-isopropyl amine,
N, accelerine, N, one of N- diethylaniline and pyridine or several combinations.
Further, the solvent is non-protonic solvent；Still further preferably, the non-protonic solvent be benzene,
One of toluene, halogenated hydrocarbons and ethyl acetate or several combinations；Still more preferably, the halogenated hydrocarbons includes two
Chloromethanes, dichloroethanes or chloroform.
Further, the reaction temperature is -10 ~ 10 DEG C；Much further preferably from -10 ~ 0 DEG C.
Further, the catalyst and substrate ethylene glycol molar ratio are 2：1.
Further, it needs first to be washed with deionized to neutrality before the mother liquor solvent evaporated that the filtering desalination obtains,
Then dry with anhydrous sodium sulfate.
Further, the purification purification uses recrystallize with dichloromethane technique, and recrystallize with dichloromethane technique belongs to existing
There is technology, details are not described herein.
Compared with prior art, it is raw material that the invention patent, which is based on ethylene glycol and chlorosulfuric acid, is directly synthesized under base catalysis
Sulfuric acid vinyl ester, production process step is few, and easy to be easy to control, raw material is easy to get, and product only needs to recrystallize, and production cost is low, the three wastes
It is few.
Specific embodiment
Below by embodiment the present invention is described in detail, it should be understood that these embodiments are only used for the purpose of illustration,
It is never limited in protection scope of the present invention.It will be understood by those skilled in the art that without departing from spirit of the invention and outside
Can be with the details and forms of the technical scheme of the invention are modified or replaced under enclosing, but these modifications or substitutions each fall within this hair
In bright protection scope.
Embodiment 1
62g is added in reaction flask（1mol）Ethylene glycol, dimethylaniline 242g（2mol）, chloroform 1000mL, temperature is cold
But -10 DEG C are arrived, lower dropwise addition chlorosulfuric acid 135g is stirred（1mol）, control temperature is no more than 0 DEG C.After being added dropwise, insulation reaction 1 is small
When.The dimethylaniline dihydrochloride generated is filtered, mother liquor is washed with deionized to neutrality, after anhydrous sodium sulfate drying, steams
Dry solvent obtains light yellow solid 101g, obtains white products 94g with recrystallize with dichloromethane, is by liquid-phase chromatographic analysis product
Sulfuric acid vinyl ester, yield 75.8%.Fusing point：95-97℃.GC purity assay：99.5%.
Embodiment 2
Ethylene glycol 62g is added in reaction flask（1mol）, triethylamine 222g（2.2mol）, methylene chloride 1000mL, temperature cooling
To -10 DEG C, lower dropwise addition chlorosulfuric acid 135g is stirred（1mol）, control temperature is no more than 0 DEG C.After being added dropwise, insulation reaction 1 is small
When.The triethylamine hydrochloride generated is filtered, mother liquor is washed with deionized to neutrality, after anhydrous sodium sulfate drying, is evaporated molten
Agent obtains light yellow solid 87g.White products 78g is obtained with recrystallize with dichloromethane.It is sulfuric acid by liquid-phase chromatographic analysis product
Vinyl acetate, yield 63%.Fusing point：95-97℃.GC purity assay：99.48%.
Embodiment 3
Ethylene glycol 62g is added in reaction flask（1mol）, pyridine 200g（2.5mol）, dichloroethanes 1000mL, temperature is cooled to-
10 DEG C, stir lower dropwise addition chlorosulfuric acid 135g（1mol）, control temperature is no more than 0 DEG C.After being added dropwise, insulation reaction 1 hour.It crosses
The pyridine hydrochloride generated is filtered, mother liquor is washed with deionized to neutrality, and after anhydrous sodium sulfate drying, solvent evaporated is obtained shallowly
Yellow solid 97g.White products 87g is obtained with recrystallize with dichloromethane.It is sulfuric acid vinyl ester by liquid-phase chromatographic analysis product, receives
Rate 70.2%.Fusing point：95-97℃.GC purity assay：99.6%.
Embodiment 4
Ethylene glycol 310g is added in reaction flask（5mol）, triethylamine 1100g（10.9mol）, methylene chloride 5000mL, temperature is cold
But -15 DEG C are arrived, lower dropwise addition chlorosulfuric acid 690g is stirred（5.1mol）, control temperature is no more than -5 DEG C.After being added dropwise, insulation reaction
2 hours.The triethylamine hydrochloride generated is filtered, mother liquor is washed with deionized to neutrality, after anhydrous sodium sulfate drying, is evaporated
Solvent obtains light yellow solid 443g.White products 393g is obtained with recrystallize with dichloromethane.It is by liquid-phase chromatographic analysis product
Sulfuric acid vinyl ester, yield 63.4%.Fusing point：95-97℃.GC purity assay：99.5%.
Embodiment 5
Ethylene glycol 310g is added in reaction flask（5mol）, pyridine 900g（11.4mol）, ethyl acetate 3000mL, temperature cooling
To -20 DEG C, lower dropwise addition chlorosulfuric acid 690g is stirred（5.1mol）, control temperature is no more than -10 DEG C.After being added dropwise, insulation reaction 3
Hour.The pyridine hydrochloride generated is filtered, mother liquor is washed with deionized to neutrality, after anhydrous sodium sulfate drying, is evaporated molten
Agent obtains light yellow solid 482g.White products 435g is obtained with recrystallize with dichloromethane.It is sulphur by liquid-phase chromatographic analysis product
Vinyl acetate, yield 70.1%.Fusing point：95-97℃.GC purity assay：99.4%.
Embodiment 6
Ethylene glycol 62g is added in reaction flask（1mol）, triethylamine 222g（2.2mol）, methylene chloride 1000mL, temperature cooling
To -40 DEG C, lower dropwise addition chlorosulfuric acid 135g is stirred（1mol）, control temperature is no more than -30 DEG C.After being added dropwise, insulation reaction 2 is small
When.The triethylamine hydrochloride generated is filtered, mother liquor is washed with deionized to neutrality, after anhydrous sodium sulfate drying, is evaporated molten
Agent obtains light yellow solid 92g.White products 83g is obtained with recrystallize with dichloromethane.It is sulfuric acid by liquid-phase chromatographic analysis product
Vinyl acetate, yield 67%.Fusing point：95-97℃.GC purity assay：99.52%.
Embodiment 7
Ethylene glycol 62g is added in reaction flask（1mol）, pyridine 126g（1.6mol）, dichloroethanes 1000mL, temperature is cooled to-
20 DEG C, stir lower dropwise addition chlorosulfuric acid 135g（0.8mol）, control temperature is no more than -10 DEG C.After being added dropwise, insulation reaction 1.5
Hour.The pyridine hydrochloride generated is filtered, mother liquor is washed with deionized to neutrality, after anhydrous sodium sulfate drying, is evaporated molten
Agent obtains light yellow solid 65g.White products 49g is obtained with recrystallize with dichloromethane.It is sulfuric acid by liquid-phase chromatographic analysis product
Vinyl acetate, yield 49%（It is calculated by chlorosulfuric acid）.Fusing point：95-97℃.GC purity assay：99.32%.
Embodiment 8
62g is added in reaction flask（1mol）Ethylene glycol, dimethylaniline 242g（2mol）, dichloroethanes 1000mL, temperature adds
Heat stirs lower dropwise addition chlorosulfuric acid 135g to 40 DEG C（1mol）, control temperature is no more than 50 DEG C.After being added dropwise, insulation reaction 1 is small
When.The dimethylaniline dihydrochloride of production is filtered, mother liquor is washed with deionized to neutrality, after anhydrous sodium sulfate drying, steams
Dry solvent obtains light yellow solid 42g, obtains white products 29g with recrystallize with dichloromethane.It is by liquid-phase chromatographic analysis product
Sulfuric acid vinyl ester, yield 23.4%.Fusing point：95-97℃.GC purity assay：99.6%.
It is compared by embodiment 1-8 as it can be seen that the effect of embodiment 1 is best, and excessively high or cross the equal shadow of low reaction temperatures
The yield for ringing reaction, it is best to comprehensively consider -10-0 DEG C of effects；And above-described embodiment is merely illustrative of the technical solution of the present invention
Rather than limit, other modifications or equivalent replacement that those of ordinary skill in the art make technical solution of the present invention, as long as
The spirit and scope for not departing from technical solution of the present invention, are intended to be within the scope of the claims of the invention.
Claims (10)
1. a kind of sulfuric acid vinyl ester synthesis technology, which is characterized in that include the following steps：
（1）Ethylene glycol reacts under the action of solvent and basic catalyst with chlorosulfuric acid；The throwing of the ethylene glycol and chlorosulfuric acid
Expect that molar ratio is 1：0.8~2；The basic catalyst is organic amine, and catalyst and substrate ethylene glycol molar ratio are 1 ~ 4：1；
The reaction temperature is at -40 ~ 50 DEG C；
（2）Filtering desalination obtains mother liquor after the reaction was completed, obtains crude product sulfuric acid vinyl ester after the mother liquor solvent evaporated；
（3）The crude product sulfuric acid vinyl ester obtains target product by refining purification.
2. sulfuric acid vinyl ester synthesis technology according to claim 1, which is characterized in that the organic amine is tertiary amine.
3. sulfuric acid vinyl ester synthesis technology according to claim 2, which is characterized in that the organic amine is triethylamine, three
Isopropylamine, N, accelerine, N, one of N- diethylaniline and pyridine or several combinations.
4. sulfuric acid vinyl ester synthesis technology according to claim 1, which is characterized in that the solvent is that aprotic is molten
Agent.
5. sulfuric acid vinyl ester synthesis technology according to claim 4, which is characterized in that the non-protonic solvent be benzene,
One of toluene, halogenated hydrocarbons and ethyl acetate or several combinations.
6. sulfuric acid vinyl ester synthesis technology according to claim 5, which is characterized in that the halogenated hydrocarbons includes dichloromethane
Alkane, dichloroethanes or chloroform.
7. sulfuric acid vinyl ester synthesis technology according to claim 1, which is characterized in that the reaction temperature is -10 ~ 10
℃。
8. sulfuric acid vinyl ester synthesis technology according to claim 1, which is characterized in that the catalyst and substrate ethylene glycol
Molar ratio is 1.6-2.5：1；The reaction temperature is -10 ~ 0 DEG C.
9. sulfuric acid vinyl ester synthesis technology according to claim 1, which is characterized in that the mother liquor that the filtering desalination obtains
It needs first to be washed with deionized before solvent evaporated to neutrality, it is then dry with anhydrous sodium sulfate.
10. sulfuric acid vinyl ester synthesis technology according to claim 1, which is characterized in that the purification purification uses dichloro
Methane recrystallizing technology.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776487A (en) * | 2019-02-26 | 2019-05-21 | 武汉松石科技股份有限公司 | A kind of preparation method of sulfuric acid vinyl ester |
| CN110818674A (en) * | 2019-11-25 | 2020-02-21 | 九江天赐高新材料有限公司 | Preparation method of vinyl sulfate |
| CN113444066A (en) * | 2021-07-21 | 2021-09-28 | 佳尔科生物科技南通有限公司 | Preparation method of vinyl sulfate |
| CN113683626A (en) * | 2020-05-19 | 2021-11-23 | 张家港市国泰华荣化工新材料有限公司 | Preparation and purification method of erythritol sulfate |
| CN114195737A (en) * | 2020-09-17 | 2022-03-18 | 张家港市国泰华荣化工新材料有限公司 | 5- (phenyl) -1,3,2, 4-dioxathiazole 2-oxide and preparation thereof |
| CN114591289A (en) * | 2022-03-29 | 2022-06-07 | 中南大学 | Preparation method of vinyl sulfate |
| CN115745950A (en) * | 2022-11-22 | 2023-03-07 | 山东兴文工业技术研究院有限公司 | Method for continuously preparing ethylene sulfite by tubular reactor |
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| CN106187989A (en) * | 2016-07-26 | 2016-12-07 | 张家港瀚康化工有限公司 | The preparation method of sulfuric acid vinyl ester |
| CN107629032A (en) * | 2017-10-25 | 2018-01-26 | 上海康鹏科技有限公司 | A kind of preparation method of cyclic sulfates |
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| CN106187989A (en) * | 2016-07-26 | 2016-12-07 | 张家港瀚康化工有限公司 | The preparation method of sulfuric acid vinyl ester |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776487A (en) * | 2019-02-26 | 2019-05-21 | 武汉松石科技股份有限公司 | A kind of preparation method of sulfuric acid vinyl ester |
| CN109776487B (en) * | 2019-02-26 | 2021-09-24 | 武汉松石科技股份有限公司 | Preparation method of vinyl sulfate |
| CN110818674A (en) * | 2019-11-25 | 2020-02-21 | 九江天赐高新材料有限公司 | Preparation method of vinyl sulfate |
| CN113683626A (en) * | 2020-05-19 | 2021-11-23 | 张家港市国泰华荣化工新材料有限公司 | Preparation and purification method of erythritol sulfate |
| CN114195737A (en) * | 2020-09-17 | 2022-03-18 | 张家港市国泰华荣化工新材料有限公司 | 5- (phenyl) -1,3,2, 4-dioxathiazole 2-oxide and preparation thereof |
| CN113444066A (en) * | 2021-07-21 | 2021-09-28 | 佳尔科生物科技南通有限公司 | Preparation method of vinyl sulfate |
| CN114591289A (en) * | 2022-03-29 | 2022-06-07 | 中南大学 | Preparation method of vinyl sulfate |
| CN114591289B (en) * | 2022-03-29 | 2023-08-25 | 中南大学 | Preparation method of vinyl sulfate |
| CN115745950A (en) * | 2022-11-22 | 2023-03-07 | 山东兴文工业技术研究院有限公司 | Method for continuously preparing ethylene sulfite by tubular reactor |
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Application publication date: 20181116 |