CN108822073A - A kind of preparation method and applications of sulfuric acid vinyl ester - Google Patents
A kind of preparation method and applications of sulfuric acid vinyl ester Download PDFInfo
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- CN108822073A CN108822073A CN201810631491.8A CN201810631491A CN108822073A CN 108822073 A CN108822073 A CN 108822073A CN 201810631491 A CN201810631491 A CN 201810631491A CN 108822073 A CN108822073 A CN 108822073A
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- sulfuric acid
- vinyl ester
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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
- C07D327/10—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms two oxygen atoms and one sulfur atom, e.g. cyclic sulfates
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Abstract
The present invention relates to a kind of preparation method and applications of sulfuric acid vinyl ester.Using ethylene sulfite as raw material, water is reaction medium, and metal and/or metal oxide are catalyst, and ozone is oxidant, is made through catalytic oxidation.The present invention has the characteristics that yield is high, easy to operate, post-processing is simple, there are no pollution to the environment.
Description
Technical field
The invention belongs to the field of chemical synthesis, are specifically related to a kind of preparation method of sulfuric acid vinyl ester.
Background technique
It is higher and higher for the performance requirement of electrochmical power source with the development of the electronics and information industry in China.Lithium-ion electric
Pond by feat of it is small in size, have a safety feature, be light-weight, pollution-free the advantages that, become the main power source of portable electronic device.Lithium
Battery can discharge heat, battery performance is caused to reduce in charge and discharge process.In the prior art by the way that sulphur is added into electrolyte
Vinyl acetate additive, to improve the battery performance under high-temperature condition.The existing sulfuric acid vinyl ester method for preparing is：By sulfurous acid second
Enester is oxidized to sulfuric acid vinyl ester in the inorganic oxides system such as potassium permanganate, periodate and hypochlorite.There are the problem of
It is that the post-processing of product is more troublesome and product purity is lower, to influence the performance and used life of lithium battery.Separately there is document
The method of the synthesis sulfuric acid vinyl ester of report, reaction equation are as follows：
Oxidant is made with the hypochlorous acid in liquor natrii hypochloritis, it in organic solvent, will be sub- under the catalytic action of ruthenium compound
Sulfuric acid vinyl ester oxidation, is then layered, and is washed, and vacuum distillation finally obtains sulfuric acid vinyl ester.In synthesis sulfurous acid ethylene
When ester, organic matter is used as solvent, the shortcomings that it is low that there is oxidation efficiencies, product purification difficult.
Summary of the invention
The object of the present invention is to provide one kind to be simple and efficient, and product is single pure, is suitble to the synthesis sulfuric acid of industrialized production
The method of vinyl acetate.
The technical solution adopted by the present invention is that：A kind of preparation method of sulfuric acid vinyl ester, includes the following steps：With sulfurous acid
Vinyl acetate is raw material, and water is reaction medium, and metal and/or metal oxide are catalyst, and ozone is oxidant, through catalysis oxidation
Reaction is made.
A kind of preparation method of above-mentioned sulfuric acid vinyl ester, the catalyst are Fe, Cu, Ni, Al, Al2O3、CuO、
FeO、NiO、MnO2With two or more the combination of MnO.Preferably, the catalyst is CuO, NiO and Al2O3It presses
Mass ratio 1：0.85：1.3 combination.Preferably, the catalyst is Cu, NiO, MnO2In mass ratio 1：1.2：0.8 group
It closes.Preferably, the catalyst is Fe, MnO and Al2O3In mass ratio 1：1.1：0.9 combination.Preferably, the catalysis
Agent is CuO, MnO and Al2O3In mass ratio 1：1.2：0.9 combination.
A kind of preparation method of above-mentioned sulfuric acid vinyl ester, the ozone are gaseous state.Ozone uses the side of surface contact
Formula is added.
A kind of preparation method of sulfuric acid vinyl ester, includes the following steps：By ethylene sulfite, distilled water and catalyst,
It being slowly stirred uniformly, at 0-20 DEG C of temperature of control, is passed through ozone, reacts 30-100min, stratification takes organic layer, it washs,
Obtain target product.Preferably, 0-5 DEG C of temperature is controlled.Preferably, ozone is passed through in the form of the mixed gas of ozone and air, smelly
Oxygen content is 20mL/L；The flow that is passed through of ozone is 0.05L/min.
The beneficial effects of the invention are as follows：
1, of the invention, using water as reaction medium, ozone is oxidant, and two kinds of substances are all environment-friendly types, at low cost to be easy to obtain
The substance obtained so that reaction process is not only environmentally friendly, but also post-processes simple.
2, of the invention, in order to increase reaction efficiency, the metal and/or metal oxide catalyst being added in reaction system are
Powder or Granular forms are added, and by the way of being slowly stirred, ultimately generate sulfuric acid vinyl ester.
3, using method of the invention, yield is high, pollution-free, and convenient for operation, the content of sulfuric acid vinyl ester is reachable in product
95% or so.
4, of the invention, solid catalyst can be directly filtered to remove after ozone oxidation, and reaction product is single pure.
5, the excessive ozone of method for the sulfuric acid vinyl ester that the present invention synthesizes can use active carbon or hopcalite agent catalysis point
Solution, it is also possible to which Production by Catalytic Combustion Process decomposes ozone.
Specific embodiment
Below by specific embodiment, the invention will be further described, but the present invention is not only defined in these examples.
Embodiment 1
Take 108.2g (1mol) ethylene sulfite, 200ml distilled water and 0.2g powder catalyst (in mass ratio,
CuO:NiO:Al2O3=1：0.85：1.3) it, is slowly stirred uniformly, controlled at ozone 0.05L/min (ozone at 5 DEG C, is passed through
Concentration is 20mL/L), it reacts 45 minutes.After reaction, stratification takes organic layer, and organic layer is washed with distilled water twice,
It is dry, obtain sulfuric acid vinyl ester, yield 94.53%.Product is through liquid-phase chromatographic analysis, the results showed that, the content of sulfuric acid vinyl ester
94.36%, the content of ethylene sulfite is 5.52%.
Embodiment 2
Take 216.3g (2mol) ethylene sulfite, 200 milliliters of distilled water and 0.4g pellet type catalyst (in mass ratio,
Cu:NiO:MnO2=1：1.2：0.8) it, is slowly stirred uniformly, controlled at ozone 0.05L/min at 5 DEG C, is passed through, (ozone is dense
Degree is 20mL/L), react 45min.After reaction, stratification, takes organic layer, and organic layer is washed with distilled water twice, does
It is dry, obtain sulfuric acid vinyl ester, yield 95.84%.Product is through liquid-phase chromatographic analysis, the results showed that, the content of sulfuric acid vinyl ester
95.63%, ethylene sulfite content 4.28%.
Embodiment 3
Take 2.161kg (2mol) ethylene sulfite, 2L distilled water and 4g powder catalyst (in mass ratio, Fe:MnO:
Al2O3=1：1.1：0.9) it, is slowly stirred uniformly, controlled at ozone 0.05L/min at 5 DEG C, is passed through, (ozone concentration is
20mL/L), 60min is reacted, after reaction, stratification takes organic layer, and organic layer is washed with distilled water twice, and it is dry, it obtains
Sulfuric acid vinyl ester, yield 95.17%.Product is through liquid-phase chromatographic analysis, the results showed that, sulfuric acid vinyl ester content 95.13% is sub-
Sulfuric acid vinyl ester content 4.68%.
Embodiment 4
Take 6.483kg (6mol) ethylene sulfite, 6L distilled water and 20g powder catalyst (in mass ratio, CuO:
MnO:Al2O3=1：1.2：0.9) it, is slowly stirred uniformly, controlled at ozone 0.05L/min (ozone concentration at 5 DEG C, is passed through
For 20mL/L), 100min is reacted, after reaction, stratification takes organic layer, and organic layer is washed with distilled water twice, does
It is dry, obtain sulfuric acid vinyl ester, yield 95.20%.Product is through liquid-phase chromatographic analysis, the results showed that, sulfuric acid vinyl ester content
95.16%, ethylene sulfite content 4.62%.
Embodiment 5
Take 108.2g (1mol) ethylene sulfite, 200ml distilled water and 0.2g powder catalyst (by quality respectively
Than CuO:NiO:Al2O3=1：0.85：1.3) it, is slowly stirred uniformly, respectively controlled at 0 DEG C, 5 DEG C, 10 DEG C, 15 DEG C, 20
DEG C and 25 DEG C at, be passed through ozone 0.05L/min (ozone concentration 20mL/L), react 45 minutes.After reaction, it stands and divides
Layer takes organic layer, and organic layer is washed with distilled water twice, dry, obtains sulfuric acid vinyl ester.Product is through liquid-phase chromatographic analysis, as a result
Such as table 1.
Table 1
| 0℃ | 5℃ | 10℃ | 15℃ | 20℃ | 25℃ | |
| Sulfuric acid vinyl ester yield % | 95.83 | 94.53 | 92.66 | 85.51 | 68.70 | 53.31 |
| The content % of sulfuric acid vinyl ester | 95.74 | 94.36 | 92.58 | 85.36 | 68.55 | 53.02 |
| The content % of ethylene sulfite | 4.19 | 5.42 | 7.20 | 14.52 | 31.16 | 46.42 |
Claims (10)
1. a kind of preparation method of sulfuric acid vinyl ester, which is characterized in that include the following steps：Using ethylene sulfite as raw material,
Water is reaction medium, and metal and/or metal oxide are catalyst, and ozone is oxidant, is made through catalytic oxidation.
2. a kind of preparation method of sulfuric acid vinyl ester according to claim 1, which is characterized in that the catalyst is
Fe、Cu、Ni、Al、Al2O3、CuO、FeO、NiO、MnO2With two or more the combination of MnO.
3. a kind of preparation method of sulfuric acid vinyl ester according to claim 2, which is characterized in that the catalyst is
CuO, NiO and Al2O3In mass ratio 1：0.85：1.3 combination.
4. a kind of preparation method of sulfuric acid vinyl ester according to claim 2, which is characterized in that the catalyst is
Cu, NiO and MnO2In mass ratio 1：1.2：0.8 combination.
5. a kind of preparation method of sulfuric acid vinyl ester according to claim 2, which is characterized in that the catalyst is
Fe, MnO and Al2O3In mass ratio 1：1.1：0.9 combination.
6. a kind of preparation method of sulfuric acid vinyl ester according to claim 2, which is characterized in that the catalyst is
CuO, MnO and Al2O3In mass ratio 1：1.2：0.9 combination.
7. a kind of preparation method of sulfuric acid vinyl ester according to claim 1-6, which is characterized in that including as follows
Step：It by ethylene sulfite, water and catalyst, is slowly stirred uniformly, at 0-20 DEG C of temperature of control, is passed through ozone, reacts 30-
100min, stratification take organic layer, and washing obtains target product.
8. a kind of preparation method of sulfuric acid vinyl ester according to claim 7, which is characterized in that include the following steps：It will
Ethylene sulfite, water and catalyst are slowly stirred uniformly, at 0-5 DEG C of temperature of control, are passed through ozone, are reacted 30-100min,
Stratification takes organic layer, and washing obtains target product.
9. a kind of preparation method of sulfuric acid vinyl ester according to claim 7 or 8, which is characterized in that the ozone
Concentration is 20mL/L, and the flow that is passed through of ozone is 0.05L/min.
10. according to the sulfuric acid vinyl ester of method described in any one of claims 1-6 preparation as additive in lithium ion battery
Application in electrolyte.
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| CN201810631491.8A CN108822073B (en) | 2018-06-19 | 2018-06-19 | Preparation method and application of vinyl sulfate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109988145A (en) * | 2019-05-13 | 2019-07-09 | 福建博鸿新能源科技有限公司 | A kind of preparation method of sulfuric acid vinyl ester |
| CN114685424A (en) * | 2020-12-25 | 2022-07-01 | 浙江蓝天环保高科技股份有限公司 | Preparation method of vinyl dithionate |
| CN115215834A (en) * | 2022-08-29 | 2022-10-21 | 长沙创新药物工业技术研究院有限公司 | Preparation method of vinyl sulfate |
| CN115504959A (en) * | 2022-10-22 | 2022-12-23 | 山东师范大学 | Safe and clean synthesis method of vinyl sulfate |
| CN116351413A (en) * | 2023-02-24 | 2023-06-30 | 无锡威孚环保催化剂有限公司 | Catalyst for synthesizing vinyl sulfate and preparation method of vinyl sulfate |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109988145A (en) * | 2019-05-13 | 2019-07-09 | 福建博鸿新能源科技有限公司 | A kind of preparation method of sulfuric acid vinyl ester |
| CN109988145B (en) * | 2019-05-13 | 2021-05-28 | 福建博鸿新能源科技有限公司 | Preparation method of vinyl sulfate |
| CN114685424A (en) * | 2020-12-25 | 2022-07-01 | 浙江蓝天环保高科技股份有限公司 | Preparation method of vinyl dithionate |
| CN114685424B (en) * | 2020-12-25 | 2023-09-05 | 浙江蓝天环保高科技股份有限公司 | Preparation method of vinyl dithionate |
| CN115215834A (en) * | 2022-08-29 | 2022-10-21 | 长沙创新药物工业技术研究院有限公司 | Preparation method of vinyl sulfate |
| CN115215834B (en) * | 2022-08-29 | 2023-12-12 | 长沙创新药物工业技术研究院有限公司 | Preparation method of vinyl sulfate |
| CN115504959A (en) * | 2022-10-22 | 2022-12-23 | 山东师范大学 | Safe and clean synthesis method of vinyl sulfate |
| CN115504959B (en) * | 2022-10-22 | 2023-06-27 | 山东师范大学 | Synthesis method of vinyl sulfate |
| CN116351413A (en) * | 2023-02-24 | 2023-06-30 | 无锡威孚环保催化剂有限公司 | Catalyst for synthesizing vinyl sulfate and preparation method of vinyl sulfate |
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