KR102681729B1 - Method for manufacturing 4-hydroxy-1,2-oxathiolane 2,2-dioxide and additive for secondary battery electrolyte manufactured using it as an intermediate - Google Patents

Abstract

A method for producing 4-hydroxy-1,2-oxathiorein 2,2-dioxide is provided. According to this, the solvent used is environmentally friendly, reaction under harsh conditions such as high temperature is unnecessary, the synthesis process is simple, the reaction time required for production of the target material is short, and the yield of the target material obtained is high, making it very suitable for mass production. do.

Description

Method for manufacturing 4-hydroxy-1,2-oxathiolane 2,2-dioxide and additive for secondary battery electrolyte manufactured using the same as an intermediate {Method for manufacturing 4-hydroxy-1,2-oxathiolane 2,2-dioxide and additive for secondary battery electrolyte manufactured using it as an intermediate}

The present invention relates to a method for producing 4-hydroxy-1,2-oxathiorein 2,2-dioxide and an additive for secondary battery electrolytes prepared using the same as an intermediate.

Recently, as lithium-ion secondary batteries have been adopted in various mobile electronic devices and electric vehicles for which demand and supply are rapidly increasing, the demand for higher-capacity and more stable lithium-ion secondary batteries is increasing, and Oxathiorane is being developed to meet the required performance accordingly. Interest and research are rapidly increasing in cyclic sulfone esters such as 2,2-dioxide and their derivatives.

Oxathiorein 2,2-dioxide or derivatives based on these are compounds known not only as additives for electrolyte solutions in lithium-ion secondary batteries, but also as pharmaceutical intermediates and photoresist materials. Looking at the function of oxathiorene 2,2-dioxide or materials containing it in the lithium ion secondary battery, when used as an additive to a non-aqueous electrolyte, it suppresses the reduction decomposition reaction of the electrolyte on the negative electrode and responds to high temperature conditions. It is known to prevent a decrease in battery capacity during charging and discharging, suppress gas generation due to decomposition of electrolyte, and prolong cycle life.

The method for producing cyclically unsaturated/saturated sultones such as oxathiorein 2,2-dioxide is to bromide sodium allylsulfonate, which can be obtained conventionally by reacting allyl bromide with sodium sulfite, to obtain a dibromo derivative, and then produce a dibromo derivative under acidic conditions. Several methods have been disclosed, such as a method of obtaining 2-bromo-1,3-propanesultone by performing a cyclization reaction under a cyclization reaction and then obtaining oxathiorein 2,2-dioxide by dehydrobromination, but these methods have been disclosed on a laboratory scale. In addition, there were problems such as not being suitable for mass production, the cost of materials being high, or the product being different from what was disclosed or not being sufficiently obtained.

Republic of Korea Patent Publication No. 10-2008-0000595

The present invention was developed in consideration of the above points. The solvent used is environmentally friendly, reaction under harsh conditions such as high temperature is unnecessary, the synthesis process is simple, the reaction time required for production of the target material is short, and the yield is short. This is about a method for producing 4-hydroxy-1,2-oxathiorein 2,2-dioxide, which is very suitable for mass production due to the high yield of the target material.

In order to solve the above-described problems, the present invention (1) reacts a compound represented by the following formula 1 and a compound represented by the formula 2 in a solvent to produce 4-hydroxy-1,2-oxathiorene 2,2-dioxide. 4-hydroxy-1,2-oxathiorein 2, including the step of synthesizing and (2) separating and obtaining the synthesized 4-hydroxy-1,2-oxathiorene 2,2-dioxide, A method for producing 2-dioxide is provided.

[Formula 1]

[Formula 2]

[M][ClO] _x

M is an alkali metal or alkaline earth metal, and x is the valence of element M.

According to one embodiment of the present invention, step (1) may be performed in the presence of a catalyst containing ruthenium chloride and an acid.

Additionally, the solvent may include water as a main agent.

Additionally, step (1) can be performed by reacting the compound represented by Formula 1 and the compound represented by Formula 2 at a molar ratio of 1:0.8 to 4.

Additionally, step (1) may be performed at a temperature of 23 to 27°C for 2 to 5 hours.

Additionally, the compound represented by Formula 2 in step (1) may be sodium hypochlorite.

Additionally, step (1) may be performed by adding the compound represented by Formula 2 while the compound represented by Formula 1 is mixed with an acid substance.

In addition, it may further include maintaining the 4-hydroxy-1,2-oxathiorein 2,2-dioxide isolated after step (2) at a temperature of 0 to 10°C.

In addition, the present invention provides a secondary battery electrolyte additive synthesized using 4-hydroxy-1,2-oxathiorein 2,2-dioxide prepared according to an embodiment of the present invention as an intermediate.

In the method for producing 4-hydroxy-1,2-oxathiorein 2,2-dioxide according to the present invention, the solvent used is environmentally friendly, reaction under harsh conditions such as high temperature is not required, the synthesis process is simple, and the target substance is The reaction time required for production is short and the yield of the target material is high, so it is very suitable for mass production. Therefore, it is widely used to manufacture cyclically unsaturated/saturated sultones and various derivatives based on them known in various industrial fields using the target material as an intermediate material. It can be applied.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. The present invention may be implemented in many different forms and is not limited to the embodiments described herein.

4-Hydroxy-1,2-oxathiorein 2,2-dioxide according to an embodiment of the present invention is obtained by (1) reacting a compound represented by Formula 1 and a compound represented by Formula 2 in a solvent to produce 4- Including the steps of synthesizing hydroxy-1,2-oxathiorein 2,2-dioxide and (2) separately obtaining the synthesized 4-hydroxy-1,2-oxathiorein 2,2-dioxide. can be manufactured.

In step (1) of the present invention, the step of synthesizing 4-hydroxy-1,2-oxathiorein 2,2-dioxide by reacting a compound represented by Formula 1 and a compound represented by Formula 2 in a solvent. Perform.

[Formula 1]

[Formula 2]

[M][ClO] _x

M is an alkali metal or alkaline earth metal, and x is the valence of element M.

Step (1) is a step of synthesizing 4-hydroxy-1,2-oxathiorein 2,2-dioxide. It is synthesized through one-pot and is a one-step reaction through reactants to obtain the target 4 -Hydroxy-1,2-oxathiorane 2,2-dioxide can be synthesized, which can be compared to any of the conventionally known synthesis methods for 4-hydroxy-1,2-oxathiorane 2,2-dioxide. It is also a very simplified method and can secure sufficient yield, making it very suitable for mass production.

Step (1) includes a compound represented by Formula 1 and a compound represented by Formula 2 as reactants. The compound represented by Formula 2, which is one of the reactants, may preferably be sodium hypochlorite or calcium hypochlorite, and more preferably may be sodium hypochlorite in terms of yield.

Additionally, in step (1), the compound represented by Formula 1 and the compound represented by Formula 2 may be mixed at a molar ratio of 1:0.8 to 4, more preferably 1:1 to 3, thereby ensuring a sufficient yield. It may be advantageous to: If the number of moles of the compound represented by Formula 2 is less than 0.8 times the number of moles of the compound represented by Formula 1, it may be difficult to secure the desired yield when mixing. In addition, if the number of moles of the compound represented by Formula 2 exceeds 4 times the number of moles of the compound represented by Formula 1, the material cost increases, it is environmentally unfavorable due to the generation of halogen gas during the reaction, and the halogen element is substituted. There is a risk that the production of products may increase.

Additionally, step (1) may be performed in the presence of a catalyst containing ruthenium chloride and an acid substance to promote the reaction. The catalyst may contain ruthenium chloride, and may contain 0.1 to 2 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the compound represented by Formula 1, through which the reaction rate and It is advantageous for improving efficiency.

Additionally, the acid substance is a substance involved in the cyclization reaction and may be, for example, hydrochloric acid, sulfuric acid, or nitric acid, and is preferably hydrochloric acid.

In addition, according to one embodiment of the present invention, in step (1), the catalyst and acid material may participate in the reaction by first mixing with the compound represented by Formula 1, and the compound represented by Formula 2 or the mixed solution is added to the mixed solution. The reaction can be performed by adding a solution containing the compound represented by Formula 2, which can be advantageous for obtaining 4-hydroxy-1,2-oxathiorein 2,2-dioxide in high yield. If the mixing step of the acid catalyst is different, it may be difficult to obtain 4-hydroxy-1,2-oxathiorein 2,2-dioxide in sufficient yield.

Meanwhile, step (1) may be performed under a solvent. The solvent may be used without limitation if it is capable of appropriately dissolving the compound represented by Formula 1 and the compound represented by Formula 2 but does not react with the reactant. For example, the solvent may include water and/or an organic solvent. However, according to one embodiment of the present invention, the solvent may include water as the main agent. Here, the main substance means that it contains more than 50% by volume of the input solvent, for example, more than 60% by volume, or more than 70% by volume. More preferably, the solvent may not contain any additional organic solvents other than water. This simplifies the solvent used, reduces material costs, and has the advantage of being environmentally friendly. Meanwhile, water as a solvent may be added in a dissolved state of the compound represented by Formula 2. Additionally, some of it may be included in the injected acid material.

Additionally, step (1) may be performed at a temperature of 20 to 40°C for 2 to 12 hours, more preferably at a temperature of 23 to 27°C for 2 to 5 hours, through which 4-hydroxy-1,2 -It is advantageous for increasing the yield of oxathiorein 2,2-dioxide. If the reaction temperature is less than 20°C, there is a risk that the reaction time may be extended or the yield may be reduced. In addition, when the reaction temperature exceeds 40°C, the instability of the 4-hydroxy-1,2-oxathiorein 2,2-dioxide produced increases and the yield may decrease. Additionally, if the reaction time exceeds 12 hours or is less than 2 hours, there is a risk that the yield may decrease.

Next, the step (2) of the present invention is to separate and obtain the synthesized 4-hydroxy-1,2-oxathiorein 2,2-dioxide.

Step (2) is a step of isolating the synthesized 4-hydroxy-1,2-oxathiorein 2,2-dioxide produced in step (1), and may further undergo purification and crystallization steps. The synthesized 4-hydroxy-1,2-oxathiorein 2,2-dioxide can be isolated by known methods.

Specifically, step (2) includes adding an isolating solvent to the mixed solution in which the reaction has been completed in step (1), separating the aqueous layer after standing for a predetermined time, and vacuum concentrating the separated aqueous layer to form 4-hydroxy- It may include the step of obtaining 1,2-oxathiorein 2,2-dioxide.

The isolation solvent may include, for example, ethyl acetate. Additionally, it can be left standing for 30 minutes to 2 hours after adding the isolating solvent. At this time, step (2) is preferably performed at 0 to 10°C. This is due to the instability of the product 4-hydroxy-1,2-oxathiorein 2,2-dioxide. If step (2) is performed at a temperature exceeding 10°C, the final yield and There is a risk that purity may decrease, and the separation process time may be extended when performed at a temperature below 0°C. In addition, step (2) is cooled from the performance temperature of step (1) to the performance temperature of step (2) at a cooling rate of 1 to 5°C/min, more preferably 3 to 5°C/min. It is good, and it can be advantageous to further improve the yield of the target product. In addition, vacuum concentration may be performed by a known method, for example, a rotary vacuum concentrator may be used, but is not limited thereto.

In addition, according to one embodiment of the present invention, it may further include maintaining the 4-hydroxy-1,2-oxathiorein 2,2-dioxide isolated after step (2) at a temperature of 0 to 10°C. You can. As described above, this is due to the instability of the desired 4-hydroxy-1,2-oxathiorein 2,2-dioxide. If the temperature is outside the above-mentioned temperature range, the isolated 4-hydroxy-1,2-oxathione There is a risk that the purity of Lane 2,2-dioxide may be lowered.

4-Hydroxy-1,2-oxathiorein 2,2-dioxide prepared by the above-described production method can be used as an intermediate to synthesize additives for secondary battery electrolytes.

As an example, the additive for secondary battery electrolyte may be a known compound used as an additive for secondary battery electrolyte whose basic skeleton is oxathiorein 2,2-dioxide. An example of this is 4-((dimethyl(vinyl)silyl)oxy)-1,2-oxathiorene 2,2-dioxide, 4-((dimethyl(2-ethanenitrile)silyl)oxy)-1,2 -It may be oxathiorein 2,2-dioxide, oxathiorein 2,2-dioxide, 5H-1,2-oxathiole 2,2-dioxide, etc.

The present invention will be described in more detail through the following examples, but the following examples do not limit the scope of the present invention, and should be interpreted to aid understanding of the present invention.

<Example 1>

Hydrochloric acid (267.9 g) as an acid was added into a 3L round flask, and then the compound represented by Formula 1 was slowly added. At this time, the compound represented by Formula 1 (374.5 g) and hydrochloric acid were mixed in a ratio of 1:3 equivalents. Afterwards, a 10% by weight aqueous solution of sodium hypochlorite (2686.3 g) as a compound represented by Formula 2 was slowly added dropwise over 12 hours while maintaining 33°C to 37°C, and the added sodium hypochlorite was equal to 1 mole of the compound represented by Formula 1. It was added to make 3 moles per sugar. After completion of the reaction, the reaction mixture was cooled at a cooling rate of 1.5°C/min, and ethyl acetate (490g) was added as an isolating solvent at 15°C. After standing for 1 hour, the aqueous layer was separated. The solvent was removed from the separated aqueous layer using a rotary vacuum concentrator, and 4-hydroxy-1,2-oxathiorein 2,2-dioxide (100 g, yield 50%) ( ¹ H NMR (400 MHz, DMSO-d6) δ (ppm): 5.95 (d, 1H), 4.74 (m, 1H), 4.52 (m, 1H), 4.27 (m, 1H), 3.68 (m, 1H), 3.27 (m, 1H)) were obtained.

<Examples 2 to 10>

Prepared in the same manner as in Example 1, but changing the type, reaction temperature, or reaction time of the compound represented by Chemical Formula 2 as shown in Table 1 below, 4-hydroxy-1,2-oxathiorane 2,2-dioxide was prepared. was obtained.

(Level 1 (2) step transference number Compound represented by formula 2 operating temperature reaction time operating temperature Example 1 sodium hypochlorite 33℃~37℃ 12 hours 15℃ 50% Example 2 sodium hypochlorite 23℃~27℃ 3 hours 15℃ 72% Example 3 sodium hypochlorite 23℃~27℃ 3 hours 6℃ 84% Example 4 sodium hypochlorite 23℃~27℃ 12 hours 15℃ 52% Example 5 sodium hypochlorite 28℃~32℃ 3 hours 15℃ 63% Example 6 sodium hypochlorite 28℃~32℃ 12 hours 15℃ 53% Example 7 Calcium hypochlorite 33℃~37℃ 12 hours 15℃ 42% Example 8 Calcium hypochlorite 23℃~27℃ 3 hours 15℃ 62% Example 9 Calcium hypochlorite 23℃~27℃ 12 hours 15℃ 41% Example 10 Calcium hypochlorite 28℃~32℃ 3 hours 15℃ 52% Example 11 Calcium hypochlorite 28℃~32℃ 12 hours 15℃ 40%

As can be seen in Table 1,

Compared to Examples 7 to 11, in which calcium hypochlorite was used, the compound represented by Formula 2 was produced in Examples 1 to 6, in which sodium hypochlorite was used, in higher yields under the same manufacturing method as 4-hydroxy-1,2. -It can be seen that oxathiorein 2,2-dioxide was obtained.

Although one embodiment of the present invention has been described above, the spirit of the present invention is not limited to the embodiment presented in the present specification, and those skilled in the art who understand the spirit of the present invention can add components within the scope of the same spirit. , other embodiments can be easily proposed by change, deletion, addition, etc., but this will also be said to be within the scope of the present invention.

Claims (9)

(1) synthesizing 4-hydroxy-1,2-oxathiorein 2,2-dioxide by reacting a compound represented by Formula 1 and a compound represented by Formula 2 in a solvent; and
(2) Separating and obtaining synthesized 4-hydroxy-1,2-oxathiorane 2,2-dioxide; Method for producing 4-hydroxy-1,2-oxathiorane 2,2-dioxide, including: :
[Formula 1]

[Formula 2]
[M][ClO] _x
M is an alkali metal or alkaline earth metal, and x is the valence of element M. According to paragraph 1,
Step (1) is a method for producing 4-hydroxy-1,2-oxathiorein 2,2-dioxide, which is performed in the presence of a catalyst containing ruthenium chloride and an acid substance. According to paragraph 1,
A method for producing 4-hydroxy-1,2-oxathiorein 2,2-dioxide wherein the solvent includes water as the main agent. According to paragraph 1,
Step (1) is a method for producing 4-hydroxy-1,2-oxathiorein 2,2-dioxide, which is performed by reacting the compound represented by Formula 1 and the compound represented by Formula 2 at a molar ratio of 1: 0.8 to 4. In paragraph 1,
Step (1) is a method for producing 4-hydroxy-1,2-oxathiorein 2,2-dioxide, which is performed at a temperature of 23 to 27°C for 2 to 5 hours. According to paragraph 1,
The compound represented by Formula 2 in step (1) is a method of producing 4-hydroxy-1,2-oxathiorein 2,2-dioxide, which is sodium hypochlorite. According to paragraph 1,
Step (1) is performed by adding the compound represented by Formula 2 while the compound represented by Formula 1 is mixed with an acid substance. Dioxide production method. According to paragraph 1,
(2) maintaining the isolated 4-hydroxy-1,2-oxathiorein 2,2-dioxide at a temperature of 0 to 10°C; 4-hydroxy-1,2-oxa Thiorene 2,2-dioxide production method. delete