CN112574167B

CN112574167B - Preparation method of methylene methanedisulfonate

Info

Publication number: CN112574167B
Application number: CN202011438029.XA
Authority: CN
Inventors: 李军; 张钊; 冯绍全; 赵青山; 宫振山; 衣凯华; 韦俨珊
Original assignee: Yantai Haichuan Chemical Co ltd
Current assignee: Yantai Haichuan Chemical Co ltd
Priority date: 2020-12-07
Filing date: 2020-12-07
Publication date: 2021-11-09
Anticipated expiration: 2040-12-07
Also published as: CN112574167A

Abstract

The invention discloses a preparation method of methylene methanedisulfonate, which takes methylene disulfonyl chloride and dichloromethane as raw materials, carbonate as an oxygen donor, 4-dimethylaminopyridine as a catalyst, and the methylene methanedisulfonate is obtained after the reaction for 12-36h at the temperature of 0-50 ℃ and recrystallization. The raw material for synthesizing the methylene methanedisulfonate is cheap and easy to obtain, the cost for producing the methylene methanedisulfonate is low, the economic benefit is higher, phosphorus pentoxide is not required to be used, viscous phosphoric acid is not generated, and the treatment of phosphate is avoided; the invention adopts dichloromethane as a reaction raw material, adopts carbonate as an oxygen donor, does not use paraformaldehyde, and avoids generating formaldehyde wastewater which is difficult to treat; the method has the advantages of mild reaction process conditions, simple and safe operation process, high product yield, short production period, higher purity of the obtained product and capability of meeting the application requirements of lithium batteries.

Description

Preparation method of methylene methanedisulfonate

Technical Field

The invention relates to organic synthesis, in particular to a preparation method of methylene methanedisulfonate.

Background

The battery added with the Methylene Methanedisulfonate (MMDS) has good high-temperature cycle performance, is suitable for power batteries, particularly power batteries taking lithium manganate as a positive electrode material, can prevent Mn melted at high temperature from being adsorbed on the surface of a negative electrode by the MMDS, inhibits impedance from rising, effectively improves cycle characteristics, and can greatly prolong the cycle life of the battery.

Patent CN101426776 (sumitomo corporation) uses solid methylene disulfonic acid and paraformaldehyde as reaction raw materials, and the MMDS is obtained by a reaction at 120 ℃ for 10 hours, and is a solvent-free solid-phase reaction, which is difficult to control, insufficient in reaction and low in yield. The synthetic route of the patent is as follows:

CN101511782 (Wako pure chemical industries, Ltd.) uses sulfuryl chloride to react with silver carbonate, and the obtained silver sulfonate reacts with diiodomethane to obtain the product MMDS. Silver carbonate and diiodomethane are expensive and not suitable for mass production. The synthetic route is as follows:

CN 10246464649 (institute of Fujian materials Structure, Chinese academy of sciences), the process takes methylene disulfonic acid and paraformaldehyde as raw materials, adopts phosphorus pentoxide as a dehydrating agent, and adopts a ball milling way for reaction, so that the amplification of the feeding amount is limited to a certain extent, and the industrialization has a great problem.

CN101511782A (Wako pure chemical industries, Ltd.) used for preparing methylene methanedisulfonate by reacting pyridinium methanedisulfonate with methylene bis (chlorosulfonate), the raw materials were not easily available, the cost was high, and the color of the obtained product was poor.

The existing methylene methanedisulfonate synthesis process is not suitable for industrial production, and the development of the methylene methanedisulfonate synthesis method suitable for industrial production has important economic and social benefits.

Disclosure of Invention

The invention provides a preparation method of methylene methanedisulfonate, aiming at the problem of low efficiency of the existing methylene methanedisulfonate synthesis, the method takes methylene disulfonyl chloride and dichloromethane as raw materials, carbonate as an oxygen donor, 4-Dimethylaminopyridine (DMAP) as a catalyst, the methylene methanedisulfonate is reacted for 12-36h at the temperature of 0-50 ℃, and the methylene methanedisulfonate is obtained after recrystallization, wherein the synthetic route is as follows:

in the method, the molar ratio of methylene disulfonyl chloride to methylene dichloride to carbonate is controlled to be 1 (1-6) to (2-4), and the molar ratio of methylene disulfonyl chloride to 4-dimethylamino pyridine is controlled to be 1 (0.005-0.5). The carbonate is one or more of cesium carbonate, potassium carbonate or sodium carbonate.

The invention has the beneficial effects that: the raw material for synthesizing the methylene methanedisulfonate is cheap and easy to obtain, the cost for producing the methylene methanedisulfonate is low, the economic benefit is higher, phosphorus pentoxide is not required to be used, viscous phosphoric acid is not generated, and the treatment of phosphate is avoided; the invention adopts dichloromethane as a reaction raw material, adopts carbonate as an oxygen donor, does not use paraformaldehyde, and avoids generating formaldehyde wastewater which is difficult to treat; the method has the advantages of mild reaction process conditions, simple and safe operation process, high product yield, short production period, higher purity of the obtained product and capability of meeting the application requirements of lithium batteries.

Drawings

FIG. 1 is a GC-MS spectrum of methylene methanedisulfonate obtained in example 1.

FIG. 2 is a DSC chart of methylene methanedisulfonate obtained in example 2.

FIG. 3 is a 13C NMR spectrum of methylene methanedisulfonate obtained in example 3.

FIG. 4 is a 1HNMR map of the methylene methanedisulfonate product prepared in example 4.

Detailed Description

The present invention is described below with reference to examples, which are provided for illustration only and are not intended to limit the scope of the present invention.

Example 1

A preparation method of methylene methanedisulfonate comprises the following specific operation steps: weighing 70.3g of methylenedisulfonyl chloride, 112.1g of dichloromethane, 91.2g of potassium carbonate and 1.6g of DMAP, adding into a 500ml three-necked bottle, introducing a dry stable nitrogen flow, stirring the reaction system at 10 ℃ for 12 hours, and filtering; 200g of dimethyl carbonate is used for extracting a filter cake, insoluble substances are removed by filtration, the filtrate is distilled to remove the solvent until white solid is separated out, and then the temperature is reduced to 5 ℃, the mixture is stirred for 0.5h and filtered, so that 42.4g of white crystal methylene methanedisulfonate is obtained.

99.7% by GC detection, and 68.3% yield. Melting point 148.05-153.02 ℃.

¹HNMR (400MHZ, deuterated acetone) delta (ppm) 5.82(s,2H),6.19(s, 2H); 13CNMR (100MHZ, deuterated acetone) delta (ppm) 68.76,91.76 HRMS (ESI) for C2H4O6S2, calcd:188, found:188.

Example 2

A preparation method of methylene methanedisulfonate comprises the following specific operation steps: 42.6g of methylene disulfonyl chloride, 67.9g of dichloromethane, 53g of sodium carbonate and 1.2g of DMAP are weighed and added into a 500ml three-necked bottle, a dry stable nitrogen flow is introduced, and the reaction system is stirred for 12 hours at 30 ℃ and then filtered; extracting the filter cake with 230g of ethyl acetate, filtering to remove insoluble substances, distilling the filtrate to remove the solvent until white solid is separated out, cooling to-5 ℃, stirring for 0.5h, filtering, and drying the filter cake to obtain 23.8g of white crystal methylene methanedisulfonate.

99.6% by GC detection, and 63.2% yield. Melting point 148.05-153.02 ℃.

Example 3

A preparation method of methylene methanedisulfonate comprises the following specific operation steps: weighing 70.3g of methylene disulfonyl chloride, 168.2g of dichloromethane, 268.8g of cesium carbonate and 2.0g of DMAP, adding into a 500ml three-necked bottle, introducing a dry stable nitrogen flow, stirring the reaction system at 40 ℃ for 12 hours, and filtering; extracting the filter cake with 400g of ethyl acetate, filtering to remove insoluble substances, distilling the filtrate to remove the solvent until white solid is separated out, cooling to-10 ℃, stirring for 0.5h, filtering, and drying the filter cake to obtain 48.2g of white crystal methylene methanedisulfonate.

The GC detection rate is 99.7 percent, and the yield is 77.6 percent. Melting point 148.05-153.02 ℃.

Example 4

A preparation method of methylene methanedisulfonate comprises the following specific operation steps: weighing 106.5g of methylenedisulfonyl chloride, 254.8g of dichloromethane, 172.8g of potassium carbonate and 3.1g of DMAP, adding into a 1000ml three-neck bottle, introducing a dry stable nitrogen flow, stirring the reaction system at 40 ℃ for 12 hours, and filtering; extracting a filter cake by using 300g of dimethyl carbonate, filtering to remove insoluble substances, distilling the filtrate to remove the solvent until white solid is separated out, cooling to 5 ℃, stirring for 0.5h, filtering, and drying the filter cake to obtain 67.8 white crystal methylene methanedisulfonate.

The GC detection rate is 99.7%, and the yield is 72.1%. Melting point 148.05-153.02 ℃.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims

1. A preparation method of methylene methanedisulfonate is characterized in that methylene disulfonyl chloride and dichloromethane are used as raw materials, carbonate is used as an oxygen donor, 4-dimethylaminopyridine is used as a catalyst, the raw materials react for 12-36 hours at the temperature of 0-50 ℃, and the methylene methanedisulfonate is obtained after recrystallization;

the molar ratio of the methylene disulfonyl chloride to the methylene dichloride to the carbonate is 1 (1-6) to 2-4;

the carbonate is one or more of cesium carbonate, potassium carbonate or sodium carbonate.

2. The method of claim 1, wherein the molar ratio of methylenedisulfonyl chloride to 4-dimethylaminopyridine is 1 (0.005-0.5).