Method for preparing cyclic sulfate by directly oxidizing hydrogen peroxide

Abstract

The method comprises the following steps: dropwise adding hydrogen peroxide into a mixture of cyclic sulfite, an organic solvent and a solid catalyst to carry out catalytic oxidation reaction, filtering out the solid catalyst after the reaction is finished, standing filtrate for layering, taking an organic layer, and performing distilling and concentrating to obtain a cyclic sulfate product. Cheaphydrogen peroxide is used for directly catalyzing and oxidizing cyclic sulfite to prepare cyclic sulfate, so that on one hand, the reaction is mild and easy to control, and the reaction conversion rate is high; on the other hand, no waste salt is generated, the evaporation capacity of water is small, energy consumption is low, generated waste water is little, and the production process is more environmentally friendly; the used solid catalyst contains an active component, an active auxiliary agent and an oxide carrier, and can be recycled, so that the consumption of noble metals is reduced, and the production cost is greatly reduced; the cyclic sulfate prepared by the method is few in impurities, high in purity and wide in market prospect.

Description

technical field [0001] The invention relates to the technical field of new energy material synthesis, in particular to a method for preparing cyclic sulfate by direct oxidation of hydrogen peroxide. The cyclic sulfate prepared by the method can be used as an additive for lithium-ion battery electrolyte, and can also be used for drug synthesis intermediates. Background technique [0002] With the enhancement of people's awareness of environmental protection and the advancement of science and technology, people pay more and more attention to new green energy technologies, especially lithium-ion secondary batteries, due to their characteristics such as high working voltage, small size, light weight, high energy density, The advantages of low environmental pollution, small self-discharge, long cycle life and no memory effect have attracted the attention of the battery industry and been widely used. As an additive for lithium-ion battery electrolyte, cyclic sulfate can effective...

AI Technical Summary

Problems solved by technology

[0008] The first is the oxidation of cyclic sulfites with hypochlorite to obtain the corresponding cyclic sulfates (Wang P., ChunB; Rachakonda S. et al., J.Org.Chem. 2009, 74, 6819-6824; KR102080198B1), although sodium hypochlorite (calcium) has strong oxidizing properties, it is extremely unstable, especially the content of active oxygen is low, the amount of wastewater is large, and the by-product sodium chloride or calcium chloride is difficult to recycle and can only be treated as solid waste , increasing the pressure on environmental protection, and is highly corrosive to equipment; on the other hand, the introduction of chlorine-containing oxidants has the potential risk of increasing impurities, which also increases the difficulty of product purification in the later stage and downstream use

[0009] The second is to oxidize cyclic sulfites with sodium periodate to obtain corresponding cyclic sulfates (Paddon-JonesG.C., Mcerulean C.S.P., Hayes P.et al, J.Org.Chem., 2001, 66, 7487-7695; Shao H., Rueter J.k., Goodman M., J.Org.Chem., 1998, 63, 5240-5244; Zhang L.Luo S., MiX.etal., Orange & Biomolecular Chemistry, 2009, 74, 6819 -6824), the method is that sodium periodate is extremely expensive on the one hand, and the cost is too high, and can only be prepared as a reagent in the laboratory, and cannot realize industrialization; on the other hand, there are many iodo impurities in the product, which affects the later stage. application

[0010] The third is to oxidize cyclic sulfite with potassium permanganate to obtain the corresponding cyclic sulfate (Berridge M.S, Franceschini M.P., Rosenfeld E.et al, J.Org.Chem., 1990,55,1211-1217) , the method has many side reactions, low yield and difficult product purification

[0011] The fourth is to adopt potassium hydrogen persulfate compound salt to oxidize cyclic sulfuric acid ester (CN103012386A, CN104744427A), although this method is mild in reaction, easy to control, but the cost of oxidizing agent is high, and the sulfate amount of by-product is relatively large

Although this method can reduce the treatment cost of sulfate by-products, due to the use of sulfuric acid, it is also highly corrosive to equipment, and the amount of waste water from evaporating brine is relatively large, and the cost of waste water treatment is high.

In addition, the above-mentioned reactions still use precious metals as catalysts, and the catalysts cannot be recycled and reused, resulting in large consumption of precious metals and high production costs.

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