CN112375064B - Vinyl sulfate synthesis process - Google Patents
Vinyl sulfate synthesis process Download PDFInfo
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- CN112375064B CN112375064B CN202011246798.XA CN202011246798A CN112375064B CN 112375064 B CN112375064 B CN 112375064B CN 202011246798 A CN202011246798 A CN 202011246798A CN 112375064 B CN112375064 B CN 112375064B
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a synthesis process of vinyl sulfate, which comprises the following steps: dissolving ethylene glycol in an organic solvent, then dropwise adding thionyl chloride, after dropwise adding, reacting at the temperature of 5-10 ℃ for 1-1.5 h in a heat preservation manner, then adding a sodium carbonate solution to adjust the pH value to 7-8, and standing for layering to obtain a mixed solution containing the ethylene sulfite; adding a catalyst into the mixed solution containing the vinyl sulfite, then dropwise adding 70% tert-butyl alcohol peroxide aqueous solution for 0.5-1 h, reacting at 30-40 ℃ for 1-3 h after dropwise adding, then adding sodium sulfite solution, standing for layering, extracting in a water phase, combining organic phases, concentrating under reduced pressure, and recrystallizing to obtain the vinyl sulfate. The process flow is simplified by directly carrying out oxidation reaction on the mixed solution containing the ethylene sulfite; the cost is further reduced by adopting 70 percent of tert-butyl peroxide aqueous solution and copper chloride; the obtained vinyl sulfate has higher yield and purity.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a synthesis process of vinyl sulfate.
Background
The ethylene sulfate is a novel organic film forming additive with excellent effect for the electrolyte of the secondary lithium ion battery. However, since the central sulfur atom of the vinyl sulfate ester has stronger electronegativity and is more reductive than the corresponding carbonate at the graphene negative electrode interface, a more stable fixed electrolyte phase interface film is formed in preference to the electrode interface. The vinyl sulfate added into the lithium battery electrolyte can inhibit the reduction of the initial capacity of the battery, increase the initial discharge capacity, reduce the expansion of the battery after being placed at high temperature, improve the charge and discharge performance of the battery and increase the cycle number.
At present, the synthesis process of the vinyl sulfate mainly comprises the following steps:
1. the reaction of sulfur trioxide and ethylene oxide is adopted to obtain the vinyl sulfate. The method is a gas phase reaction, and has high danger and high requirement on equipment.
2. The method comprises the steps of reacting thionyl chloride with ethylene glycol to obtain sulfite, and oxidizing the ethylene sulfite to obtain ethylene sulfate. The method generates a large amount of hydrogen chloride gas, the corrosion to equipment is large, meanwhile, the catalyst generally adopts noble metals, and the cost of the catalyst is high.
Disclosure of Invention
In view of the above, it is necessary to provide a vinyl sulfate synthesis process to solve the technical problem of high cost of the existing synthesis process in the prior art.
The first aspect of the invention provides a synthesis process of vinyl sulfate, which comprises the following steps:
dissolving ethylene glycol in an organic solvent, then dropwise adding thionyl chloride, after dropwise adding, carrying out heat preservation reaction at the temperature of 5-10 ℃ for 1-1.5 h, then adding a sodium carbonate solution to adjust the pH value to 7-8, and standing and layering to obtain a mixed solution containing ethylene sulfite;
adding a catalyst into the mixed solution containing the vinyl sulfite, then dropwise adding 70% tert-butyl alcohol peroxide aqueous solution for 0.5-1 h, reacting at 30-40 ℃ for 1-3 h after dropwise adding, then adding sodium sulfite solution, standing for layering, extracting a water phase, combining organic phases, concentrating under reduced pressure, and recrystallizing to obtain the vinyl sulfate.
Compared with the prior art, the invention has the beneficial effects that:
the invention simplifies the process flow by directly carrying out the oxidation reaction on the mixed solution containing the ethylene sulfite; meanwhile, 70% of tert-butyl peroxide aqueous solution is used as an oxidant and copper chloride is used as a catalyst, so that the cost is further reduced; the obtained vinyl sulfate has higher yield and purity.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a synthesis process of vinyl sulfate, which comprises the following steps:
s1 substitution reaction: dissolving ethylene glycol in an organic solvent, then dropwise adding thionyl chloride, after dropwise adding, carrying out heat preservation reaction at the temperature of 5-10 ℃ for 1-1.5 h, then adding a sodium carbonate solution to adjust the pH value to 7-8, and standing and layering to obtain a mixed solution containing ethylene sulfite; wherein the organic solvent is one or more of dichloromethane, dichloroethane and chloroform; the mass ratio of the ethylene glycol to the organic solvent is 1: (2-5), preferably 1: 4; the molar ratio of the ethylene glycol to the thionyl chloride is 1: (1.3-1.5), preferably 1: 1.4; in the dropping process, the temperature of the system is controlled to be 0-5 ℃, and the dropping time is 1-2 h.
S2 oxidation reaction: and adding copper chloride into the mixed solution containing the vinyl sulfite, then dropwise adding 70% of tert-butyl alcohol peroxide aqueous solution for 0.5-1 h, reacting at 30-40 ℃ for 1-3 h after dropwise adding, then adding sodium sulfite solution, standing for layering, extracting in an aqueous phase, combining organic phases, concentrating under reduced pressure, and recrystallizing to obtain the vinyl sulfate. Wherein the molar ratio of the glycol to the tert-butyl peroxide is 1: (1.5-2); the molar ratio of ethylene glycol to catalyst is 1: (0.03-0.05); in the recrystallization process, the solvent adopted is n-hexane.
The specific synthetic route is as follows:
the sodium carbonate solution added in the substitution reaction process can remove the unreacted thionyl chloride completely, is more favorable for the stability of the ethylene sulfite and reduces byproducts; meanwhile, a water layer can be removed through a simple standing and layering process to obtain a ethylene sulfite layer; the substitution reaction product is added with the organic solvent, the reaction temperature is strictly controlled, the generation of byproducts is reduced, the mixed solution containing the ethylene sulfite is directly used as the raw material of the oxidation reaction after standing and layering, the process is simplified, the purity of the obtained ethylene sulfate is not greatly influenced, and the yield is improved; in the oxidation reaction process, the tert-butyl alcohol peroxide aqueous solution is used as an oxidant, and the copper chloride is used as a catalyst, so that the oxidation reaction can be promoted, the catalyst cost is reduced, the reaction period is shortened, and the product yield and purity are improved; meanwhile, the tert-butyl peroxide aqueous solution is added into the reaction system in a dropwise manner, so that the reaction stability can be improved, and the production of a target product is facilitated; the proportion of each raw material, the dripping time and the reaction time in the oxidation reaction process are strictly controlled, so that the product yield is further improved; during the oxidation reaction, the unreacted tert-butyl peroxide can be removed by adding sodium sulfite solution.
Example 1
(1) And (3) substitution reaction: dissolving ethylene glycol (1mol, 62.1g) in dichloromethane (250g), and then dropwise adding thionyl chloride (1.4mol, 166.6g), wherein in the dropwise adding process, the temperature of the system is controlled to be 0-5 ℃, and the dropwise adding time is 1.5 h; after the dropwise addition, reacting for 1.2h at the temperature of 8 ℃, then adding a sodium carbonate solution to adjust the pH to 7.6, and standing and layering to obtain a mixed solution containing the ethylene sulfite;
(2) and (3) oxidation reaction: adding copper chloride (0.04mol, 5.4g) into the mixed solution containing the vinyl sulfite, then dropwise adding 70% tert-butyl peroxide aqueous solution (1.8mol, 231.4g) for 45min, reacting at 35 ℃ for 2h after dropwise adding, then adding sodium sulfite solution, standing for layering, extracting an aqueous phase, combining organic phases, concentrating under reduced pressure, and recrystallizing n-hexane to obtain the vinyl sulfate.
Example 2
(1) And (3) substitution reaction: dissolving 1mol of ethylene glycol (62.1 g) in 120g of dichloromethane, and then dropwise adding 1.3mol of thionyl chloride (154.7 g), wherein in the dropwise adding process, the temperature of the system is controlled to be 0-5 ℃, and the dropwise adding time is 2 h; after the dropwise addition is finished, reacting for 1h at the temperature of 5 ℃, then adding a sodium carbonate solution to adjust the pH value to 7, and standing for layering to obtain a mixed solution containing the ethylene sulfite;
(2) and (3) oxidation reaction: adding copper chloride (0.03mol, 4.0g) into the mixed solution containing the vinyl sulfite, then dropwise adding 70% tert-butyl peroxide aqueous solution (1.5mol, 192.9g) for 30min, reacting at 30 ℃ for 3h after the dropwise adding is finished, then adding sodium sulfite solution, standing for layering, extracting an aqueous phase, combining organic phases, concentrating under reduced pressure, and recrystallizing n-hexane to obtain the vinyl sulfate.
Example 3
(1) And (3) substitution reaction: dissolving ethylene glycol (1mol, 62.1g) in dichloromethane (310g), and then dropwise adding thionyl chloride (1.5mol, 178.5g), wherein in the dropwise adding process, the temperature of the system is controlled to be 0-5 ℃, and the dropwise adding time is 2 hours; after the dropwise addition, reacting for 1.5h at the temperature of 10 ℃, then adding a sodium carbonate solution to adjust the pH to 8, and standing and layering to obtain a mixed solution containing the ethylene sulfite;
(2) and (3) oxidation reaction: adding copper chloride (0.05mol, 6.7g) into the mixed solution containing the vinyl sulfite, then dropwise adding 70% tert-butyl peroxide aqueous solution (2mol, 257.1g) for 60min, reacting at 40 ℃ for 1h after dropwise adding, then adding sodium sulfite solution, standing for layering, extracting an aqueous phase, combining organic phases, concentrating under reduced pressure, and recrystallizing n-hexane to obtain the vinyl sulfate.
Comparative example 1
(1) And (3) substitution reaction: dissolving ethylene glycol (1mol, 62.1g) in dichloromethane (250g), and then dropwise adding thionyl chloride (1.4mol, 166.6g), wherein in the dropwise adding process, the temperature of the system is controlled to be 0-5 ℃, and the dropwise adding time is 1.5 h; after the dropwise addition is finished, reacting for 1.2h at the temperature of 8 ℃, then adding a sodium carbonate solution to adjust the pH value to 6, and standing and layering to obtain a mixed solution containing the ethylene sulfite;
(2) and (3) oxidation reaction: adding copper chloride (0.04mol, 5.4g) into the mixed solution containing the vinyl sulfite, then dropwise adding 70% tert-butyl peroxide aqueous solution (1.8mol, 231.4g) for 45min, reacting at 35 ℃ for 2h after dropwise adding, then adding sodium sulfite solution, standing for layering, extracting an aqueous phase, combining organic phases, concentrating under reduced pressure, and recrystallizing n-hexane to obtain the vinyl sulfate.
Comparative example 2
(1) Substitution reaction: dissolving ethylene glycol (1mol, 62.1g) in dichloromethane (250g), and then dropwise adding thionyl chloride (1.4mol, 166.6g), wherein in the dropwise adding process, the temperature of the system is controlled to be 0-5 ℃, and the dropwise adding time is 1.5 h; after the dropwise addition, reacting for 1.2h at the temperature of 8 ℃, then adding a sodium carbonate solution to adjust the pH to 9, and standing and layering to obtain a mixed solution containing the ethylene sulfite;
(2) and (3) oxidation reaction: adding copper chloride (0.04mol, 5.4g) into the mixed solution containing the vinyl sulfite, then dropwise adding 70% tert-butyl peroxide aqueous solution (1.8mol, 231.4g) for 45min, reacting at 35 ℃ for 2h after the dropwise adding is finished, then adding sodium sulfite solution, standing for layering, extracting an aqueous phase, combining organic phases, concentrating under reduced pressure, and recrystallizing n-hexane to obtain the vinyl sulfate.
Comparative example 3
(1) And (3) substitution reaction: dissolving 1mol of ethylene glycol (62.1 g) in 250g of dichloromethane, and then dropwise adding 1.4mol of thionyl chloride (166.6 g), wherein in the dropwise adding process, the temperature of the system is controlled to be 0-5 ℃, and the dropwise adding time is 1.5 h; after the dropwise addition, reacting for 1.2h at the temperature of 8 ℃, then adding a sodium carbonate solution to adjust the pH to 7.6, and obtaining the ethylene sulfite after standing, layering and solvent recovery by reduced pressure distillation;
(2) and (3) oxidation reaction: adding dichloromethane (250g) and copper chloride (0.04mol, 5.4g) into the above ethylene sulfite, then dropwise adding 70% tert-butyl peroxide aqueous solution (1.8mol, 231.4g) for 45min, reacting at 35 ℃ for 2h after dropwise adding, then adding sodium sulfite solution, standing for layering, extracting water phase, combining organic phase, concentrating under reduced pressure, and recrystallizing n-hexane to obtain ethylene sulfate.
Comparative example 4
(1) Substitution reaction: dissolving 1mol of ethylene glycol (62.1 g) in 250g of dichloromethane, and then dropwise adding 1.4mol of thionyl chloride (166.6 g), wherein in the dropwise adding process, the temperature of the system is controlled to be 0-5 ℃, and the dropwise adding time is 1.5 h; after the dropwise addition, reacting for 1.2h at the temperature of 8 ℃, then adding a sodium carbonate solution to adjust the pH to 7.6, and standing and layering to obtain a mixed solution containing the ethylene sulfite;
(2) and (3) oxidation reaction: adding copper chloride (0.04mol, 5.4g) into the mixed solution containing the vinyl sulfite, then adding 70% tert-butyl peroxide aqueous solution (1.8mol, 231.4g) at one time, reacting at 35 ℃ for 2.75h, then adding sodium sulfite solution, standing for layering, extracting an aqueous phase, combining organic phases, concentrating under reduced pressure, and recrystallizing n-hexane to obtain the vinyl sulfate.
TABLE 1
The yield in table 1 is the total yield of the two-step reaction.
As can be seen from Table 1, the vinyl sulfate obtained in the embodiments 1 to 3 of the present invention has high yield and purity. Compared with example 1, the substitution reaction processes of comparative example 1 and comparative example 2 respectively adopt lower and higher pH values, so that the yield and purity of the target product are lower, and probably because the pH value is too low, so that thionyl chloride in the system is not completely treated, the subsequent oxidation reaction is influenced, and the pH value is too high, so that the product is unstable. The yield of the product obtained in comparative example 3 was lower than that of example 1, probably because a small amount of vinyl sulfite was lost and the yield was lowered in the process of removing the solvent by distillation under reduced pressure after the completion of the substitution reaction in comparative example 3 to obtain vinyl sulfite. The yield and purity of the product obtained in comparative example 4 were lower compared to example 1, which may be due to instability of the system by adding the aqueous t-butyl peroxide solution all at once, ultimately affecting the yield and purity of the product.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (8)
1. A process for synthesizing vinyl sulfate is characterized by comprising the following steps:
dissolving ethylene glycol in an organic solvent, then dropwise adding thionyl chloride, after dropwise adding, carrying out heat preservation reaction at the temperature of 5-10 ℃ for 1-1.5 h, then adding a sodium carbonate solution to adjust the pH value to 7-8, and standing and layering to obtain a mixed solution containing ethylene sulfite;
adding copper chloride into the mixed solution containing the vinyl sulfite, then dropwise adding 70% tert-butyl alcohol peroxide aqueous solution for 0.5-1 h, reacting at 30-40 ℃ for 1-3 h after dropwise adding, then adding sodium sulfite solution, standing for layering, extracting in an aqueous phase, combining organic phases, concentrating under reduced pressure, and recrystallizing to obtain the vinyl sulfate.
2. The process for synthesizing vinyl sulfate according to claim 1, wherein the molar ratio of ethylene glycol to thionyl chloride is 1: (1.3-1.5).
3. The process for synthesizing vinyl sulfate according to claim 1, wherein in the process of dropwise adding the thionyl chloride, the temperature of the system is controlled to be 0-5 ℃, and the dropwise adding time is 1-2 hours.
4. The process for synthesizing vinyl sulfate according to claim 1, wherein the organic solvent is one or more of dichloromethane, dichloroethane and chloroform.
5. The process for synthesizing vinyl sulfate according to claim 1, wherein the mass ratio of the ethylene glycol to the organic solvent is 1: (2-5).
6. The process for synthesizing vinyl sulfate according to claim 1, wherein the molar ratio of ethylene glycol to t-butyl peroxide is 1: (1.5-2).
7. The process for synthesizing vinyl sulfate according to claim 1, wherein the molar ratio of ethylene glycol to copper chloride is 1: (0.03-0.05).
8. The process for synthesizing vinyl sulfate according to claim 1, wherein the solvent used in the recrystallization is n-hexane.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113683592A (en) * | 2021-08-27 | 2021-11-23 | 江苏瀚康新材料有限公司 | Preparation method of ethyl methyl carbonate solution containing ethylene sulfate |
| CN114539210A (en) * | 2022-03-19 | 2022-05-27 | 宁夏天霖新材料科技有限公司 | Method for preparing ethylene sulfite by using microchannel reactor |
| CN115745949A (en) * | 2022-10-21 | 2023-03-07 | 山东海科新源材料科技股份有限公司 | Vinyl sulfate production process |
| CN115677652A (en) * | 2022-11-14 | 2023-02-03 | 陕西煤业化工技术研究院有限责任公司 | Method for continuously preparing vinyl sulfate |
| CN115806540B (en) * | 2022-11-18 | 2024-08-30 | 荣成青木高新材料有限公司 | Preparation method of ethylene sulfite |
| CN118084857A (en) * | 2024-01-31 | 2024-05-28 | 福建省德旭新材料有限公司 | Preparation method of vinyl sulfate |
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