CN110724122A

CN110724122A - Preparation method of methylene methanedisulfonate

Info

Publication number: CN110724122A
Application number: CN201911088316.XA
Authority: CN
Inventors: 易方; 林旭锋; 易宗明
Original assignee: Hunan Asda New Materials Co Ltd
Current assignee: Hunan Asda New Materials Co Ltd
Priority date: 2019-11-08
Filing date: 2019-11-08
Publication date: 2020-01-24
Anticipated expiration: 2039-11-08
Also published as: CN110724122B

Abstract

Disclosed is a method for efficiently producing high-purity methylene methanedisulfonate with high yield. Methylene bis (chlorosulfonate), methyl disulfonic acid and pyridyl-containing resin are used as raw materials to carry out chemical reaction, and high-purity methylene methanedisulfonate can be obtained with high yield through a simple post-treatment purification process. Wherein methylene bis (chlorosulfonate) can be prepared from the reaction of dichloromethane and sulfur trioxide, and the resin containing pyridyl can be recycled. The method has the advantages of mild reaction conditions, simple and environment-friendly process, convenient operation, wide raw material source, high product yield and purity and low preparation cost. The obtained methylene methanedisulfonate can be used as an additive of the electrolyte of the power lithium battery.

Description

Preparation method of methylene methanedisulfonate

Technical Field

The invention relates to the field of organic matter chemical synthesis methods, in particular to a method for preparing high-purity methylene methanedisulfonate with high efficiency and high yield.

Background

At present, commercial production of lithium ion power batteries becomes the most concerned focus of people, and the power lithium batteries not only bring substantial progress to application in the fields of UPS, mobile laser power supplies, mobile lighting power supplies, mobile communication equipment, military and aerospace, but also bring gospel to the desire of the automobile industry to greatly replace traditional energy sources with power supplies. The lithium manganate material is used as the anode material of the power lithium ion battery, has the advantages of low price, high potential, environmental friendliness, high safety and the like, and is suitable for being applied to the field of energy storage batteries of electric tools, electric vehicles and the like; the lithium manganate and the ternary material can be mixed for use in a certain range; from the market share of lithium battery anode materials all over the world, the market share of lithium manganate is on the rise.

The Methylene Methanedisulfonate (MMDS) as the additive of the lithium battery electrolyte can enable the battery to have good high-temperature cycle performance, and is suitable for power batteries, in particular to power batteries using lithium manganate as a positive electrode material. Because the methylene methanedisulfonate can be decomposed on the surface of the LiMn2O4 electrode to form a good protective film, the film effectively reduces the decomposition of electrolyte and the dissolution of metal manganese ions in the electrolyte, obviously improves the thermal stability of the LiMn2O4 anode material, can prevent Mn melted at high temperature from being adsorbed on the surface of a cathode, inhibits the rise of impedance, effectively improves the cycle characteristic, and can greatly prolong the cycle life of the anode material. Along with the improvement of the market share of the lithium manganate battery, the market scale of the methylene methanedisulfonate is gradually enlarged, and the market prospect is wide.

In the prior art, the preparation method of methylene methanedisulfonate (CAS number: 99591-74-9) mainly comprises the following steps:

1. world patent 85/03075, which uses the reaction of methane disulfonic acid galaxediiodomethane to obtain methylene methanedisulfonate. The method has the advantages of low yield, high cost, and high concentration of metal ions in the product;

2. japanese patent JP2005-336155A discloses the preparation of methylene methanedisulfonate by a cyclization reaction of methylene methanedisulfonate with methylene diacetate. Related raw material methylene diacetate has no batch preparation method, and the product has more impurities and is difficult to purify;

3. chinese patent CN101426776 adopts methane disulfonic acid and paraformaldehyde to carry out solvent-free cyclization reaction in the presence of a dehydrating agent to prepare methylene methanedisulfonate. After the reaction of the method is finished, because of solid phase reaction, when mass production is carried out, the reaction is not sufficient, the reaction control is not easy, the obtained reaction liquid is very black and viscous, products are not easy to extract, the defects of low yield, more waste water, easy environmental pollution caused by formaldehyde and the like exist, and in addition, the obtained products have poor color and luster, more impurities and low purity;

4. chinese patent CN101511782A discloses the preparation of methylene methanedisulfonate by reacting pyridinium methanedisulfonate with methylene bis (chlorosulfonate). The method generates a large amount of organic waste pyridinium chlorosulfonate, organic alkali and onium salt (pyridinium methanedisulfonate and/or pyridinium chlorosulfonate) also remain after recrystallization of the product, if the product is washed by water, the product can be partially hydrolyzed or dissolved, and the water is difficult to remove, so that the residual water amount of the product can not reach the qualified standard, in addition, the waste water containing organic matters is greatly increased, and the obtained product has poor color and luster, more impurities and purity of less than 99 percent, and is not enough to be used as an electrolyte additive of a lithium battery.

However, the use of Methylene Methanedisulfonate (MMDS) as an electronic grade reagent as an additive for lithium battery electrolytes is a high-end ultrapure chemical, which is required to achieve a high purity of white powder or white crystals, at least a chemical purity of 99.9%, and a sufficiently low residual metal content, with a residual moisture of less than 200 ppm. Therefore, the further development of the method for preparing the high-purity methylene methanedisulfonate with high efficiency and high yield has important significance for promoting the development of the lithium ion power battery industry.

Disclosure of Invention

In view of the above-mentioned disadvantages of the prior art, the present invention provides a method for preparing methylene methanedisulfonate, so as to obtain high-purity and high-yield methylene methanedisulfonate.

In order to achieve the purpose, the invention adopts the technical scheme that:

a process for producing methylene methanedisulfonate, which comprises reacting methylenebis (chlorosulfonate), methyldisulfonic acid and a pyridyl group-containing resin in an aprotic solvent.

The preparation method of the methylene methanedisulfonate comprises the steps of uniformly mixing the methylene disulfonate and the pyridine-containing resin in an aprotic solvent, adding methylene bis (chlorosulfonate) for reaction, filtering the resin after the reaction is finished, concentrating the filtrate, and recrystallizing and refining to obtain the high-purity methylene methanedisulfonate. Wherein the filtered resin can be repeatedly used in the preparation reaction after the processes of washing, drying and the like.

One of the reaction formulae shown below:

。

the resin containing pyridyl is one or the combination of more than two of poly (4-vinylpyridine), poly (2-vinylpyridine), poly (4-vinylpyridine-co-butyl methacrylate), poly (4-vinylpyridine-co-styrene), poly (2-vinylpyridine-co-butyl methacrylate) and polyvinyl chloride-pyridine with the polymer molecular weight of more than 5000 according to any weight proportion.

CAS numbers for some resins are as follows: poly (4-vinylpyridine) 25232-41-1 or 9017-40-7, poly (2-vinylpyridine) 25014-15-7, poly (4-vinylpyridine-co-butyl methacrylate) 53761-76-5, poly (4-vinylpyridine-co-styrene) 26222-40-2, poly (2-vinylpyridine-co-styrene) 24980-54-9; poly (4-vinylpyridine) and other commercial pyridyl-containing resins having a polymer molecular weight greater than 2 million are preferred. Pyridyl-containing resins can also be prepared according to published literature methods. The commercially available resins include: poly (4-vinylpyridine) from the company welfare and Alfa, 2% cross-linked, about 60 mesh, 8.0 meq/g; poly-4-vinylpyridine, powder, anhydrous (toluenemodified) by Strem; poly (2-vinylpyridine), average Mw 5,000 (Tyfocal), average Mn 4,800 (Tyfocal), Poly (2-vinylpyridine), average Mw 37,500 (Tyfocal), average Mn 35,000 (Tyfocal), Poly (2-vinylpyridine), average Mw159,000 (Tyfocal), average Mn 152,000 (Tyfocal), by Sigma-optics.

The resin containing pyridyl has special performance, such as containing abundant basic group porous copolymer, can be an acid-binding agent, can adsorb metal ions, has large adsorption capacity, is easy to elute, and can be recycled; in addition, after the method is applied to the reaction, when the resin obtained by filtering is recycled by water washing, alkali washing and the like, the using amount of the washing liquid is controllable, and organic waste materials cannot be contained; heterogeneous reaction, and excellent swelling performance. The research progress on the synthesis performance and application of vinylpyridine resin can be seen in the following documents: ion exchange and adsorption, 2008, 24(1): 89.

The methylenebis (chlorosulfonate) can be prepared by reacting methylene chloride with sulfur trioxide, as described in U.S. patent No. 4649209 or org. biomol. chem., 2004, 2, 1554.

The aprotic solvent can be one or more of acetonitrile, dichloroethane, dichloromethane, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dioxane, tetrahydrofuran, isopropyl ether, toluene, ethyl acetate, methyl tert-butyl ether, hexamethylphosphoramide, dimethyl sulfoxide, chlorobenzene, xylene, chloroform, benzene, dimethyl carbonate, butanone, cyclohexane, N-hexane or petroleum ether in any weight ratio.

The reaction temperature is 10-150 ℃, and the reaction time is 0.5-12 hours.

The molar ratio of the methyl disulfonic acid to the methylene bis (chlorosulfonate) is 1: 0.9 to 1.1; the pyridine group-containing resin is converted to a resin containing a pyridine base functional group in a molar amount of 2 times or more the molar amount of methyldi-sulfonic acid.

Compared with the existing synthesis method, the invention has the beneficial effects that:

(1) the reaction condition is mild, and the feeding and the post-treatment are very simple;

(2) the reaction starting material is easy to obtain, and the reaction yield and yield are high;

(3) the resin containing pyridyl can be recycled, and the wastewater does not contain organic impurities;

(4) the residual quantity of water and metal ions is low, and an ultrapure product with good color and luster is easy to obtain.

Detailed Description

The invention will now be further elucidated with reference to specific embodiments. The following examples are only preferred embodiments of the present application and are not intended to limit the scope of the present invention. Any substitutions, identical or similar, which are identical or similar and do not depart from the gist of the invention, are intended to be within the scope of the invention.

Example one

To 100 ml of dichloroethane, 4 g of poly (4-vinylpyridine) [ Alfa Co., 2% crosslinked, about 60 mesh, 8.0meq/g ] was added, swelling was carried out at room temperature for 10 minutes, 2.114 g of methyldi-sulfonic acid (12 mmol) was then added, stirring was carried out at room temperature sufficiently for 1 hour, 2.94 g of methylenebis (chlorosulfonate) (12 mmol) was then added, and the mixture was heated to reflux (83 ℃ C.) and reacted for 6 hours. After the reaction, the reaction mixture was filtered, the filter cake was washed with 10 ml of dichloroethane, the filtrate was concentrated to give 2.26 g of off-white solid, and the ethyl acetate/petroleum ether was recrystallized and refined 2 times to give 2 g of methylene methanedisulfonate (yield 89%), purity 99.9%, residual moisture less than 200ppm, and no other impurities were detected. Melting point: 151.5-152.5 ℃.

Example two

The resin filtered out in example 1 was washed with 5 ml of water, 5 ml of aqueous alkali (concentration: 5 mol/l), 5 ml of water and dried to obtain 4 g of poly (4-vinylpyridine). The procedure of example 1 was followed, except that 4 g of the poly (4-vinylpyridine) recovered as above was used in place of the original fresh resin. As a result, it was found that 2.27 g of an off-white solid was obtained by concentrating the filtrate, and purification by ethyl acetate/petroleum ether recrystallization was carried out 2 times to obtain 2.05 g of methylene methanedisulfonate (yield: 91%), purity: 99.9%, residual moisture content: less than 200ppm, and no other impurities were detected. Melting point: 151.5-152.5 ℃.

EXAMPLE III

To 40 ml of N, N-dimethylformamide was added 4 g of poly (4-vinylpyridine) [ Alfa Co., 2% crosslinked, about 60 mesh, 8.0meq/g ], swollen at room temperature for 5 minutes, followed by addition of 2.114 g of methyldi-sulfonic acid (12 mmol), stirring well at room temperature for 0.5 hours, addition of 2.94 g of methylenebis (chlorosulfonate) (12 mmol), and reaction at 55 ℃ for 5 hours. After the reaction, the reaction mixture was filtered, the filter cake was washed with 10 ml of N, N-dimethylformamide, and the filtrate was concentrated under reduced pressure to give 2.27 g of an off-white solid, which was recrystallized from toluene and purified 2 times to give 2.08 g of a white crystal of methylene methanedisulfonate (yield 92%), purity 99.9%, residual water content less than 200ppm, and no other impurities were detected. Melting point: 151.5-152.5 ℃.

Example four

To 80 ml of acetonitrile, 4 g of Poly (4-vinylpyridine) [ Poly-4-vinylpyridine, powder, anhydros (tolumen-conditioning) by Strem ] was added, and the mixture was swollen at room temperature for 10 minutes, followed by addition of 2.114 g of methyldi-sulfonic acid (12 mmol), followed by stirring at room temperature sufficiently for 1 hour, addition of 2.94 g of methylenebis (chlorosulfonate) (12 mmol), and reaction at 80 ℃ for 5 hours. After the reaction, the reaction mixture was filtered, the filter cake was washed with 10 ml of acetonitrile, the filtrate was concentrated to give 2.26 g of an off-white solid, and the filtrate was recrystallized and purified 2 times from toluene to give 2.0 g of a white crystal of methylene methanedisulfonate (yield 89%), purity 99.9%, residual water content less than 200ppm, and no other impurities were detected. Melting point: 151.5-152.5 ℃.

EXAMPLE five

To 50 ml of N-methylpyrrolidone, 4 g of Poly (4-vinylpyridine) [ Poly (2-vinylpyridine) by Sigma-aldrich, average Mw 37,500 (Typical), average Mn 35,000 (Typical) ] was added, and the mixture was swollen at room temperature for 2 minutes, followed by addition of 2.114 g of methyldi-sulfonic acid (12 mmol), followed by stirring at room temperature sufficiently for 0.5 hour, addition of 2.94 g of methylenebis (chlorosulfonate) (12 mmol), and reaction at 80 ℃ for 4 hours. After the reaction, the reaction mixture was filtered, the filter cake was washed with 8 ml of N-methylpyrrolidone, the filtrate was concentrated under reduced pressure to obtain 2.25 g of an off-white solid, and the filtrate was recrystallized from toluene and purified 2 times to obtain 2.0 g of a white crystal of methylene methanedisulfonate (yield 89%), purity 99.9%, residual water content less than 200ppm, and no other impurities were detected. Melting point: 151.5-152.5 ℃.

Claims

1. A process for producing methylene methanedisulfonate, which comprises reacting methylenebis (chlorosulfonate), methyldisulfonic acid and a pyridyl group-containing resin in an aprotic solvent.

2. The method for preparing methylene methanedisulfonate according to claim 1, wherein the methylene disulfonate is prepared by uniformly mixing the methylene disulfonate and the pyridine-containing resin in an aprotic solvent, adding methylene bis (chlorosulfonate) to the mixture to react, and after the reaction is finished, filtering the resin, concentrating the filtrate, and recrystallizing the filtrate to obtain the high-purity methylene methanedisulfonate.

3. The method for preparing methylene methanedisulfonate according to claim 1, wherein the pyridyl-containing resin is selected from one or a combination of two or more of poly (4-vinylpyridine), poly (2-vinylpyridine), poly (4-vinylpyridine-co-butyl methacrylate), poly (4-vinylpyridine-co-styrene), poly (2-vinylpyridine-co-butyl methacrylate) and polyvinyl chloride-pyridine, which have a polymer molecular weight of more than 5000.

4. The method according to claim 1, wherein the aprotic solvent is one or a combination of two or more selected from acetonitrile, dichloroethane, dichloromethane, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dioxane, tetrahydrofuran, isopropyl ether, toluene, ethyl acetate, methyl tert-butyl ether, hexamethylphosphoramide, dimethylsulfoxide, chlorobenzene, xylene, chloroform, benzene, dimethyl carbonate, methyl ethyl ketone, cyclohexane, N-hexane, and petroleum ether.

5. The process for producing methylene methanedisulfonate according to claim 1, wherein the molar ratio of the methylene disulfonic acid to the methylene bis (chlorosulfonate) is 1: 0.9 to 1.1; the pyridine group-containing resin is converted to a resin containing a pyridine base functional group in a molar amount of 2 times or more the molar amount of methyldi-sulfonic acid.

6. The process for producing methylene methanedisulfonate according to claim 1, wherein the reaction temperature is 10 to 150 ℃ and the reaction time is 0.5 to 12 hours.

7. The method for producing methylene methanedisulfonate according to claim 1, 2, 3, 4, 5, or 6, wherein the resin containing a pyridyl group is repeatedly used in the reaction after the completion of one reaction, filtration, washing a plurality of times, and drying.