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WO2017064910A1 - Procédé de prévention de la décomposition du diméthylsulfoxyde - Google Patents

Procédé de prévention de la décomposition du diméthylsulfoxyde Download PDF

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Publication number
WO2017064910A1
WO2017064910A1 PCT/JP2016/073242 JP2016073242W WO2017064910A1 WO 2017064910 A1 WO2017064910 A1 WO 2017064910A1 JP 2016073242 W JP2016073242 W JP 2016073242W WO 2017064910 A1 WO2017064910 A1 WO 2017064910A1
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WO
WIPO (PCT)
Prior art keywords
dimethyl sulfoxide
decomposition
liquid containing
sodium carbonate
present
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/073242
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English (en)
Japanese (ja)
Inventor
治男 村野
勝弘 柴山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Fine Chemicals Co Ltd
Original Assignee
Toray Fine Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toray Fine Chemicals Co Ltd filed Critical Toray Fine Chemicals Co Ltd
Priority to JP2016555630A priority Critical patent/JPWO2017064910A1/ja
Publication of WO2017064910A1 publication Critical patent/WO2017064910A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/06—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/02—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms
    • C07C317/04—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton

Definitions

  • the present invention relates to a method for suppressing the decomposition of dimethyl sulfoxide (DMSO). *
  • Dimethyl sulfoxide is widely used industrially as a polymer polymerization and spinning solvent. In addition, the used dimethyl sulfoxide is widely recovered and reused. Industrially, when dimethyl sulfoxide is recovered and reused, dimethyl sulfoxide is purified by heating distillation. However, dimethyl sulfoxide is thermally relatively unstable. Dimethyl sulfoxide is known to decompose slightly when distilled at atmospheric pressure. When producing or recovering and reusing dimethyl sulfoxide by distillation, the presence of a decomposition product of dimethyl sulfoxide reduces the purity of dimethyl sulfoxide.
  • dimethyl sulfoxide can be distilled at a high temperature of 110 ° C. or higher, a high vacuum is not required at the time of distillation, no load is applied to the decompression device, and the distillation equipment is simple and industrially preferable.
  • Patent Document 1 a method of adding a metal hydroxide such as sodium hydroxide or potassium hydroxide as a decomposition inhibitor of dimethyl sulfoxide has been known (see Patent Document 1).
  • a metal hydroxide such as sodium hydroxide or potassium hydroxide
  • Patent Document 1 a method of adding a metal hydroxide such as sodium hydroxide or potassium hydroxide as a decomposition inhibitor of dimethyl sulfoxide.
  • sodium hydroxide is added to dimethyl sulfoxide and heated, decomposition of dimethyl sulfoxide may be promoted. Therefore, there is a need for a method that is safe and suppresses decomposition of dimethyl sulfoxide even at high temperatures when dimethyl sulfoxide is purified by distillation. It was done.
  • An object of the present invention is to provide a method for suppressing the decomposition of dimethyl sulfoxide by adding a safe additive that suppresses the decomposition of dimethyl sulfoxide.
  • the present invention is a method for suppressing decomposition of dimethyl sulfoxide by adding 0.0005 g to 2 g of sodium carbonate to 100 g of dimethyl sulfoxide in a liquid containing dimethyl sulfoxide under an inert gas atmosphere.
  • the method for inhibiting the decomposition of dimethyl sulfoxide according to the present invention makes it difficult for dimethyl sulfoxide to decompose even when dimethyl sulfoxide is heated to a high temperature.
  • the method of the present invention when dimethyl sulfoxide is distilled and collected, decomposition of dimethyl sulfoxide is suppressed, and high-purity dimethyl sulfoxide can be obtained by distillation. Moreover, since it can be distilled at a high temperature, a high vacuum facility is not required, so that it can be purified at low cost. Sodium carbonate is safe and can be operated safely compared to conventional decomposition control methods and purification methods that use hazardous materials.
  • the method for suppressing the decomposition of dimethyl sulfoxide according to the present invention can suppress deterioration of the quality of dimethyl sulfoxide due to, for example, long-term storage in summer and heating to melt dimethyl sulfoxide frozen in winter.
  • dimethyl sulfoxide which is a method of suppressing decomposition of dimethyl sulfoxide according to the present invention
  • dimethyl sulfoxide is used as a solvent for polymer polymerization and spinning processes of polyacrylonitrile, cellulose, polyimide, polysulfone, polyurethane and the like, and for photoresists of electronic materials. It can be used as a peeling liquid, synthesis of medicines and agricultural chemicals, a peeling / cleaning liquid for lens molds, or a peeling liquid for paints.
  • the present invention is a method for suppressing the decomposition of dimethyl sulfoxide, and sodium carbonate is added to a liquid containing dimethyl sulfoxide.
  • Sodium carbonate may be anhydrous or hydrated, and monohydrate and decahydrate that are readily available are preferable.
  • Sodium carbonate can be added as a powder or a solid. Sodium carbonate may be added as an aqueous solution. When sodium carbonate is added as an aqueous solution, for example, it can be automatically and continuously charged into a distillation apparatus or a storage container at a uniform concentration, which is preferable for safety.
  • the solubility of sodium carbonate in 100 g of water is as large as 22 g at 20 ° C. For this reason, when sodium carbonate is added to a liquid containing dimethyl sulfoxide and distilled to precipitate sodium carbonate crystals, the sodium carbonate crystals in the distillation apparatus can be easily removed by washing with water.
  • the concentration of sodium carbonate in aqueous solution can be increased to a concentration that saturates at the temperature used.
  • the concentration of sodium carbonate is preferably 0.1 to 35 g, more preferably 0.2 to 30 g with respect to 100 g of water. Even more preferably, it is 1 to 30 g. Most preferably, it is 10 to 25 g.
  • the amount of sodium carbonate added is 0.0005 g to 2 g with respect to 100 g of dimethyl sulfoxide in the liquid.
  • the amount of sodium carbonate added is preferably from 0.001 g to 1.5 g, more preferably from 0.001 g to 1 g, based on 100 g of dimethyl sulfoxide in the liquid.
  • the addition amount is less than 0.0005 g, the decomposition suppressing effect is not sufficient.
  • the solubility in water is low when the temperature is 0 ° C. or lower in the winter, so that a large amount of water is added when the aqueous solution is added.
  • the timing of adding sodium carbonate to the liquid containing dimethyl sulfoxide may be added before the distillation when the liquid containing dimethyl sulfoxide is distilled, or impurities having a boiling point lower than that of dimethyl sulfoxide are distilled off. Then, it may be added and distilled.
  • the inert gas atmosphere means a nitrogen, carbon dioxide, helium or argon atmosphere, and may be composed of one kind of gas or a mixed gas of two or more kinds of gases.
  • a nitrogen atmosphere is preferred under an inert gas atmosphere.
  • dimethyl sulfoxide when distilling a liquid containing dimethyl sulfoxide, dimethyl sulfoxide is decomposed, so that it was distilled under reduced pressure at 110 ° C. or lower.
  • the method for inhibiting the decomposition of dimethyl sulfoxide according to the present invention suppresses the decomposition of dimethyl sulfoxide even at high temperatures, and therefore does not require a high degree of vacuum when a liquid containing dimethyl sulfoxide is distilled.
  • the temperature during distillation is preferably 90 ° C. or higher and 191 ° C. or lower, more preferably 100 ° C. or higher and 180 ° C. or lower, and even more preferably 110 ° C.
  • the temperature is 170 ° C. or lower.
  • the storage temperature of the liquid containing dimethyl sulfoxide is preferably 18 ° C. or higher and 120 ° C. or lower, and more preferably 25 ° C. or higher and 100 ° C. or lower.
  • the concentration of dimethyl sulfoxide in the liquid containing dimethyl sulfoxide to be distilled is preferably 10% or more, more preferably 20% or more.
  • the concentration of dimethyl sulfoxide is lower than 10%, it may be costly to remove impurities by distillation.
  • the concentration of dimethyl sulfoxide in the liquid containing dimethyl sulfoxide is preferably 10% or more, and more preferably 20% or more.
  • the liquid containing dimethyl sulfoxide may contain water in addition to dimethyl sulfoxide.
  • a liquid containing dimethyl sulfoxide contains a resin component, an insoluble material, a component that easily gels upon heating, an impurity that promotes decomposition of an acid, a strong alkali, a component that reacts with dimethyl sulfoxide, or the like It is preferable to remove, separate, inactivate, and neutralize in advance by filtration, adsorption separation, ion exchange resin, addition of base, and the like.
  • the present invention can be applied to both batch distillation and continuous distillation when a liquid containing dimethyl sulfoxide is distilled.
  • continuous distillation it is preferable to continuously supply an aqueous sodium carbonate solution before the distillation column.
  • the distillation column when distilling a liquid containing dimethyl sulfoxide, is preferably a 1 to 50 distillation column, and more preferably a 3 to 40 distillation column.
  • sodium carbonate deposited after distillation may be disposed of, or recovered and reused.
  • sodium carbonate may be disposed of or recovered and reused.
  • analysis of the decomposition rate of dimethyl sulfoxide uses gas chromatography using a capillary column.
  • the decomposition rate of dimethyl sulfoxide after heating at 180 ° C. for 24 hours is preferably 0.06 area% or less, more preferably 0.05 area% or less, and even more preferably 0.04 area% or less.
  • the decomposition rate of dimethyl sulfoxide after heating at 157 ° C. for 5 hours is preferably 0.04 area% or less, more preferably 0.02 area% or less. Preferably, 0.01 area% or less is even more preferable.
  • the purity of dimethyl sulfoxide after heating is analyzed by gas chromatography using a capillary column.
  • the purity of dimethyl sulfoxide after 24 hours of heating at 180 ° C. is preferably 99.94% or more, and more preferably 99.95% or more.
  • the purity of dimethyl sulfoxide after heating at 157 ° C. for 5 hours is preferably 99.96% or more, more preferably 99.97% or more, More preferably, it is 98% or more.
  • the liquid containing dimethyl sulfoxide is, for example, a reaction liquid containing dimethyl sulfoxide obtained in the step of synthesis by sulfide oxidation or the like, a polymerization or spinning step of a polymer such as polyacrylonitrile, cellulose, polyimide, polysulfone, or polyurethane.
  • waste liquid containing dimethyl sulfoxide used in the above waste liquid containing dimethyl sulfoxide used as a stripping solution for photoresists of electronic materials, waste fluid containing dimethyl sulfoxide used as a stripping / cleaning solution for lens molds, etc.
  • Waste liquid containing dimethyl sulfoxide or waste liquid containing dimethyl sulfoxide used as a paint stripping solution can be obtained from the liquid containing these dimethyl sulfoxides by distillation.
  • GC purity of dimethyl sulfoxide (area%) It was measured by a gas chromatography method (hereinafter abbreviated as “GC”) under the following conditions.
  • Example 1 A 300 ml three-necked flask equipped with a Dimroth condenser, a stirrer, and a thermometer, 200 g of dimethyl sulfoxide (GC purity 99.997 area%), 0.002 g of sodium carbonate as an additive (0.001 g based on 100 g of dimethyl sulfoxide) After replacing the inside of the flask with nitrogen, a rubber balloon filled with nitrogen was attached to the top of the Dimroth condenser and sealed. Starting from the time when the internal temperature reached 178 ° C. in an oil bath at 192 ° C., heating was performed at 180 ⁇ 2 ° C. for 24 hours. After cooling to 25 ° C.
  • the liquid on the wall of the flask was mixed with the internal liquid.
  • the GC purity of this dimethyl sulfoxide was 99.966 area%.
  • Table 1 shows the decomposition rates determined from the GC purity. The oxide amount was 0.00 area%.
  • Example 1 (Examples 2 to 4) Example 1 was repeated except that the amount of sodium carbonate added was changed as described in Table 1. Table 1 shows the results of GC purity, decomposition rate, and oxide amount of dimethyl sulfoxide in each Example.
  • Example 1 Example 1 was repeated except that sodium carbonate was not added.
  • Table 2 shows the results of GC purity, decomposition rate, and oxide amount of dimethyl sulfoxide of Comparative Example 1.
  • Example 5 200 g of dimethyl sulfoxide was charged into a 300 ml three-necked flask equipped with a Dimroth condenser, a stir bar, and a thermometer. Subsequently, as an additive, an aqueous sodium carbonate solution in which 0.2 g of sodium carbonate (0.1 g with respect to 100 g of dimethyl sulfoxide) was dissolved in 14 g of distilled water (7 g with respect to 100 g of dimethyl sulfoxide) was charged. The GC purity of dimethyl sulfoxide in the case of containing water before heating was 99.997 area%.
  • Example 6 Example 5 was repeated except that the amount of sodium carbonate added was changed as described in Table 3.
  • Table 3 shows the results of GC purity of dimethyl sulfoxide when the liquid before heating and water after the heating are included, and the decomposition rate when water is included.
  • Comparative Example 9 As described in Table 3, the procedure was the same as Example 5 except that 0.1 g of sodium hydroxide was added. Table 3 shows the GC purity of dimethyl sulfoxide when the liquid before heating and the water after heating in Comparative Example 9 are included, and the decomposition rate results when water is included.
  • the present invention when a liquid containing dimethyl sulfoxide is distilled, highly pure dimethyl sulfoxide can be obtained.
  • the decomposition of dimethyl sulfoxide is a solvent for polymer polymerization and spinning processes such as polyacrylonitrile, cellulose, polyimide, polysulfone and polyurethane, and a photoresist stripping solution for electronic materials. It can be used as a pharmaceutical / agrochemical synthesis, as a peeling / cleaning solution for lens molds, or as a peeling solution for paints.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé permettant de prévenir la décomposition du diméthylsulfoxyde, ledit procédé consistant à ajouter du carbonate de sodium à hauteur de 0,0005 à 2 g par rapport aux 100 g de diméthylsulfoxyde contenus dans un liquide contenant du diméthylsulfoxyde sous une atmosphère de gaz inerte. Selon la présente invention, il devient possible de produire du diméthylsulfoxyde de pureté élevée lors de la distillation d'un liquide contenant du diméthylsulfoxyde. Selon la présente invention, il devient également possible de prévenir la détérioration de la qualité du diméthylsulfoxyde lorsque le diméthylsulfoxyde est stocké pendant une longue période pendant les mois d'été ou lorsque le diméthylsulfoxyde qui est congelé pendant les mois d'hiver est chauffé afin de faire fondre le diméthylsulfoxyde congelé.
PCT/JP2016/073242 2015-10-14 2016-08-08 Procédé de prévention de la décomposition du diméthylsulfoxyde Ceased WO2017064910A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2016555630A JPWO2017064910A1 (ja) 2015-10-14 2016-08-08 ジメチルスルホキシドの分解を抑制する方法

Applications Claiming Priority (4)

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JP2015202832 2015-10-14
JP2015-202832 2015-10-14
JP2016000909 2016-01-06
JP2016-000909 2016-01-06

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018127412A (ja) * 2017-02-08 2018-08-16 東レ・ファインケミカル株式会社 溶液の着色防止方法
WO2018189969A1 (fr) * 2017-04-12 2018-10-18 東レ・ファインケミカル株式会社 Procédé de distillation de diméthylsulfoxyde et colonne de distillation à plusieurs étages
CN113533591A (zh) * 2021-06-18 2021-10-22 山东罗欣药业集团恒欣药业有限公司 一种头孢丙烯中苯和三聚乙醛的gc分析方法
CN115991663A (zh) * 2021-10-19 2023-04-21 中国石油化工股份有限公司 一种二甲基亚砜的回收系统、回收方法及其所得二甲基亚砜

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114478330B (zh) * 2020-10-23 2024-11-01 中国石油化工股份有限公司 二甲基亚砜的回收精制方法和系统
CN113607869B (zh) * 2021-07-14 2024-06-11 北京赛升药业股份有限公司 利用气相色谱法检测安替安吉肽中残留溶剂的方法及应用

Citations (2)

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Publication number Priority date Publication date Assignee Title
JP2014224105A (ja) * 2013-04-24 2014-12-04 東レ・ファインケミカル株式会社 ジメチルスルホキシドの精製方法
JP2015145359A (ja) * 2014-01-06 2015-08-13 東レ・ファインケミカル株式会社 ジメチルスルホキシドの精製方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014224105A (ja) * 2013-04-24 2014-12-04 東レ・ファインケミカル株式会社 ジメチルスルホキシドの精製方法
JP2015145359A (ja) * 2014-01-06 2015-08-13 東レ・ファインケミカル株式会社 ジメチルスルホキシドの精製方法

Non-Patent Citations (1)

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Title
SANTOSUSSO M. THOMAS ET AL.: "Acid Catalysis in Dimethyl Sulfoxide Reactions. A Generally Unrecognized Factor", J. ORG. CHEM., vol. 41, no. 16, 1976, pages 2762 - 2768 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018127412A (ja) * 2017-02-08 2018-08-16 東レ・ファインケミカル株式会社 溶液の着色防止方法
WO2018189969A1 (fr) * 2017-04-12 2018-10-18 東レ・ファインケミカル株式会社 Procédé de distillation de diméthylsulfoxyde et colonne de distillation à plusieurs étages
US11111211B2 (en) 2017-04-12 2021-09-07 Toray Fine Chemicals Co., Ltd. Method of distilling dimethyl sulfoxide and multistage distillation tower
CN113533591A (zh) * 2021-06-18 2021-10-22 山东罗欣药业集团恒欣药业有限公司 一种头孢丙烯中苯和三聚乙醛的gc分析方法
CN113533591B (zh) * 2021-06-18 2022-08-23 山东罗欣药业集团恒欣药业有限公司 一种头孢丙烯中苯和三聚乙醛的gc分析方法
CN115991663A (zh) * 2021-10-19 2023-04-21 中国石油化工股份有限公司 一种二甲基亚砜的回收系统、回收方法及其所得二甲基亚砜

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JPWO2017064910A1 (ja) 2018-08-09
TW201726611A (zh) 2017-08-01

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