JP2018200878A - High-purity vinylene carbonate - Google Patents
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Abstract
Description
本発明は、高純度ビニレンカーボネートに関する。
ビニレンカーボネートは、リチウム二次電池用電解液の溶媒及び添加剤として有用である。
The present invention relates to high-purity vinylene carbonate.
Vinylene carbonate is useful as a solvent and an additive for an electrolytic solution for a lithium secondary battery.
ビニレンカーボネートの合成法としては、これ迄に幾つかの方法が報告されている。例えばエチレンカーボネートの塩素化で得られるクロロエチレンカーボネートの脱塩化水素による方法（Ｍ．Ｓ．Ｎｅｗｍａｎ ａｎｄ Ｒ．Ｗ．Ａｄｄｏｒ，Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，７５，１２６３（１９５３）、Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，７７，３７８９（１９５５））、特開平１１−１８０９７４号公報）やエチレンカーボネートの脱水素による方法（米国特許第３，４５７，２７９号公報）等が知られている。 Several methods have been reported so far for synthesizing vinylene carbonate. For example, a method by dehydrochlorination of chloroethylene carbonate obtained by chlorination of ethylene carbonate (MS Newman and RW Addor, J. Am. Chem. Soc., 75, 1263 (1953), J. Am). Chem. Soc., 77, 3789 (1955)), JP-A-11-180974), a method by dehydrogenation of ethylene carbonate (US Pat. No. 3,457,279) and the like are known.
電解液の溶媒として用いられるビニレンカーボネートについては、高品質のものが要求されるが、例えばクロロエチレンカーボネートを原料とするビニレンカーボネートについては、非常に多様な有機塩素化合物や無機塩素化合物を不純物として含有している。
このため、粗ビニレンカーボネートの精製方法についても、今迄に幾つかの方法が提案されている。
The vinylene carbonate used as the solvent for the electrolytic solution is required to have a high quality. For example, vinylene carbonate using chloroethylene carbonate as a raw material contains a wide variety of organic chlorine compounds and inorganic chlorine compounds as impurities. doing.
For this reason, several methods have been proposed so far for the purification of crude vinylene carbonate.
例えば、減圧条件での蒸留（Ｍ．Ｓ．Ｎｅｗｍａｎ ａｎｄ Ｒ．Ｗ．Ａｄｄｏｒ，Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，７５，１２６３（１９５３）、Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，７７，３７８９（１９５５））、融液晶析法によりビニレンカーボネートを部分的に結晶化させる操作を数回繰り返す方法（英国特許第８９９２０５号公報）とゾーンメルティングによる方法（Ｍ．Ｚｉｅｆ，Ｈ．Ｒｕｃｈ ａｎｄ Ｃ．Ｈ．Ｓｃｈｒａｍｍ，Ｊ．Ｃｈｅｍ．Ｅｄｕｃａｔｉｏｎ，４０，３５１（１９６３））及びクロロエチレンカーボネートの脱塩化水素反応をジブチルカーボネート等の高沸点溶媒中で行い、次いで蒸留する方法（特開２０００−２６４４９号公報）等が提案されている。 For example, distillation under reduced pressure conditions (MS Newman and RW Addor, J. Am. Chem. Soc., 75, 1263 (1953), J. Am. Chem. Soc., 77, 3789 (1955). )), A method in which vinylene carbonate is partially crystallized by a melt liquid crystal deposition method (UK Patent No. 899205) and a method by zone melting (M. Zief, H. Ruch and CH. Schramm, J. Chem. Education, 40, 351 (1963)) and a method in which a dehydrochlorination reaction of chloroethylene carbonate is carried out in a high boiling point solvent such as dibutyl carbonate and then distilled (Japanese Patent Laid-Open No. 2000-26449), etc. Has been proposed.
しかしながら、蒸留による精製法の場合、沸点がビニレンカーボネートに近い有機塩素化合物が製品中に不純物として混入するために品質的に満足できるものではない。
また、クロロエチレンカーボネートの脱塩化水素反応を高沸点溶媒中で行う方法については、高価な溶媒の回収が容易ではなく、工業的に満足できるものではない。
一方、融液晶析による方法については、高品質の製品を得ようとすれば、回収率を低くしなければならず、経済的に満足できるものではない。
However, in the case of the purification method by distillation, an organic chlorine compound having a boiling point close to that of vinylene carbonate is mixed in as an impurity in the product, which is not satisfactory in terms of quality.
Moreover, about the method of performing the dehydrochlorination reaction of a chloroethylene carbonate in a high boiling-point solvent, collection | recovery of an expensive solvent is not easy and is not industrially satisfactory.
On the other hand, with respect to the method by melt liquid crystal deposition, if a high-quality product is to be obtained, the recovery rate must be lowered, which is not economically satisfactory.
本発明は、高品質のビニレンカーボネートを従来の方法よりも経済的に製造することが
できる方法を提供しようとするものである。
The present invention seeks to provide a process by which high quality vinylene carbonate can be produced more economically than conventional processes.
本発明者らは、かかる事情に鑑み鋭意検討した結果、粗ビニレンカーボネート中に不純物として含まれる塩素化合物については、極性溶媒及び／又は芳香族炭化水素溶媒に溶解すること、しかもその量が少ない場合には前記溶媒中に非極性溶媒が含まれていても塩素化合物は溶解したままであること、従って、かかる溶媒を用いて粗ビニレンカーボネートの晶析精製をすれば、不純物が製品の表面に付着したり、或いはそれ自身が固体として析出するという問題は起こらず、製品品質が向上することを見出し、本発明を完成するに至った。
即ち、本発明の要旨は、純度９９．５％以上であり、塩素化合物の含有量が全塩素量として５００ｐｐｍ以下であるビニレンカーボネート、にある。
As a result of intensive studies in view of such circumstances, the present inventors have found that the chlorine compound contained as an impurity in the crude vinylene carbonate can be dissolved in a polar solvent and / or an aromatic hydrocarbon solvent, and the amount thereof is small. Even if a non-polar solvent is contained in the solvent, the chlorine compound remains dissolved. Therefore, if the crude vinylene carbonate is purified by crystallization using such a solvent, impurities will adhere to the surface of the product. Or the problem that it precipitates as a solid does not occur, and it has been found that the product quality is improved, and the present invention has been completed.
That is, the gist of the present invention resides in vinylene carbonate having a purity of 99.5% or more and a chlorine compound content of 500 ppm or less as a total chlorine content.
本発明によれば、粗ビニレンカーボネートを極性溶媒及び／又は芳香族炭化水素溶媒を含む溶媒に溶解させ、次いでビニレンカーボネートを固定として析出させることにより、高品質のビニレンカーボネートを経済的に得ることができる。 According to the present invention, it is possible to economically obtain high-quality vinylene carbonate by dissolving crude vinylene carbonate in a solvent containing a polar solvent and / or an aromatic hydrocarbon solvent, and then precipitating vinylene carbonate as a fixed substance. it can.
以下、本発明を詳細に説明する。
本発明の対象となる粗ビニレンカーボネートについては、その製造方法が限定されるものではないが、不純物として塩素化合物を含むものが好ましく、例えば前述したクロロエチレンカーボネートの脱塩化水素反応（Ｍ．Ｓ．Ｎｅｗｍａｎ ａｎｄ Ｒ．Ｗ．Ａｄｄｏｒ，Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，７５，１２６３（１９５３）、Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，７７，３７８９（１９５５））により得られたものが好ましい。
Hereinafter, the present invention will be described in detail.
The crude vinylene carbonate which is the subject of the present invention is not limited in its production method, but preferably contains a chlorine compound as an impurity. For example, the dehydrochlorination reaction (MS) of chloroethylene carbonate described above is preferable. Newman and RW Addor, J. Am. Chem. Soc., 75, 1263 (1953), J. Am. Chem. Soc., 77, 3789 (1955)) are preferred.
但し、原料となる粗ビニレンカーボネートの純度については、単蒸留等により好ましくは９５％以上、より好ましくは９７％以上迄精製したものがよい。
粗ビニレンカーボネートを溶解させる溶媒としては、極性溶媒及び／又は芳香族炭化水素溶媒、即ち、極性溶媒及び芳香族炭化水素溶媒から選ばれる少なくとも一種の溶媒が用いられる。かかる溶媒は単独でも二種以上の混合物でもよい。なお、本発明でいう「溶解」とは、粗ビニレンカーボネートと上記溶媒とがエマルジョン様に懸濁状態にあるものをも包含する。
However, the purity of the crude vinylene carbonate as a raw material is preferably purified by simple distillation or the like to 95% or more, more preferably 97% or more.
As the solvent for dissolving the crude vinylene carbonate, a polar solvent and / or an aromatic hydrocarbon solvent, that is, at least one solvent selected from a polar solvent and an aromatic hydrocarbon solvent is used. Such solvents may be used singly or as a mixture of two or more. The “dissolution” in the present invention includes those in which the crude vinylene carbonate and the solvent are in a suspension state like an emulsion.
但し、かかる溶媒については、塩素含有不純物の溶解量が、溶媒１００ｇ当り０．１ｇ以上、好ましくは１ｇ以上であるものが好ましい。
なお、粗ビニレンカーボネート中に含まれる塩素化合物とは、ビニレンカーボネートがクロロエチレンカーボネートの脱塩酸により製造された場合には、例えばクロロエチレンカーボネート、ジクロロエチレンカーボネート、クロロアセトアルデヒド、クロロエタノール、ジメトキシメチルクロライド、反応溶媒の塩素化物のような有機塩素化合物である。
However, such solvents are preferably those in which the amount of chlorine-containing impurities dissolved is 0.1 g or more, preferably 1 g or more per 100 g of solvent.
Note that the chlorine compound contained in the crude vinylene carbonate is, for example, chloroethylene carbonate, dichloroethylene carbonate, chloroacetaldehyde, chloroethanol, dimethoxymethyl chloride, reaction when vinylene carbonate is produced by dehydrochlorination of chloroethylene carbonate. Organochlorine compounds such as chlorinated solvents.
この場合、かかる非極性溶媒の具体例としては、例えばプロパン、ブタン、イソブタン、ペンタン、２−メチルブタン、ネオペンタン、シクロペンタン、ヘキサン、２−メチルペンタン、３−メチルペンタン、ヘプタン、２−メチルヘキサン、３−メチルヘキサン、シクロヘキサン、オクタン、イソオクタン、ノナン、イソノナン、デカン等が挙げられる。 In this case, specific examples of such a nonpolar solvent include propane, butane, isobutane, pentane, 2-methylbutane, neopentane, cyclopentane, hexane, 2-methylpentane, 3-methylpentane, heptane, 2-methylhexane, Examples include 3-methylhexane, cyclohexane, octane, isooctane, nonane, isononane, decane, and the like.
本発明に用いられる極性溶媒の具体例としては、例えばメタノール、エタノール、１−プロパノール、２−プロパノール、１−ブタノール、２−ブタノール、イソブタノール、ｔ−ブタノール、１−ペンタノール、２−ペンタノール、３−ペンタノール、アミルアルコール、イソアミルアルコール、１−ヘキサノール、２−ヘキサノール、３−ヘキサノール、２−メチル−２−ペンタノール、２−メチル−３−ペンタノール、３−メチル−３−ペンタノール、１−ヘプタノール、２−ヘプタノール、３−ヘプタノール、４−ヘプタノール、２−メチル−２−ヘキサノール、３−メチル−３−ヘキサノール、４−メチル−４−ヘキサノール、２−メチル−４−ヘキサノール、４−メチル−２−ヘキサノール、２−エチルヘキサノール、ベンジルアルコール、フェノール、レゾルシノール、１−フェニルエタノール、２−フェニルエタノール、１−フェニル−２−ブタノール、３−フェニル−１−ブタノール、１，２−プロパンジオール、１，３−プロパンジオール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、エチレングリコール、グリセロール等のアルコール類；エタノールアミン、プロパノールアミン、メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、メチルエチルアミン、メチルブチルアミン、プロピルアミン、ジプロピルアミン、トリプロピルアミン、ジイソプロピルアミン、トリイソプロピルアミン、ｔ−ブチルアミン、１，２−エチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル−１，２−エチレンジアミン、ジ（ｎ−ブチル）アミン、トリブチルアミン、アニリン、Ｎ−メチルアニリン、Ｎ，Ｎ−ジメチルアニリン、トルイジン、Ｎ，Ｎ−ジメチルトルイジン等のアミン類；アセトアルデヒド、ブチルアルデヒド、ヘキサナール、プロピオンアルデヒド等のアルデヒド類；ブタノン、アセトン、メチルプロピルケトン、ジエチルケトン等のケトン類；ギ酸メチル、ギ酸エチル、ギ酸プロピル、ギ酸ブチル、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、プロピオン酸メチル、γ−ブチロラクトン、プロピオン酸ブチル等のカルボン酸エステル類；ジメチルエーテル、ジエチルエーテル、メチルエチルエーテル、ジブチルエーテル、ジイソプロピルエーテル、ジオキサン、トリオキサン、テトラヒドロフラン、メチル−ｔ−ブチルエーテル、ジメトキシエタン等のエーテル類；フラン、ピロール、ピリジン、チオフェン等のヘテロ芳香族化合物；ホルムアミド、ジメチルホルムアミド、ジエチルホルムアミド、ジメチルアセトアミド、ジエチルアセトアミド、Ｎ−メチルピロリドン等のカルボキシアミド類；アセトニトリル、プロピオニトリル、ブチロニトリル等のニトリル類；クロロベンゼン、１，２−ジクロロベンゼン、１，３−ジクロロベンゼン、プロモベンゼン等のハロ芳香族化合物；臭化エチル、塩化エチル、フッ化エチル、臭化ブチル、塩化ブチル、塩化メチル、クロロホルム、ジクロロエタン、ジクロロメタン等のハロゲン化アルキル化合物；ニトロメタン、ニトロエタン、１−ニトロプロパン、２−ニトロプロパン、１−ニトロブタン、２−ニトロブタン、ニトロベンゼン、２−ニトロトルエン、３−ニトロトルエン等のニトロ化合物が挙げられる。 Specific examples of polar solvents used in the present invention include, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, and 2-pentanol. 3-pentanol, amyl alcohol, isoamyl alcohol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 2-methyl-2-hexanol, 3-methyl-3-hexanol, 4-methyl-4-hexanol, 2-methyl-4-hexanol, 4 -Methyl-2-hexanol, 2-ethylhexanol, benzyl Lucol, phenol, resorcinol, 1-phenylethanol, 2-phenylethanol, 1-phenyl-2-butanol, 3-phenyl-1-butanol, 1,2-propanediol, 1,3-propanediol, 1,2- Alcohols such as butanediol, 1,3-butanediol, 1,4-butanediol, ethylene glycol, glycerol; ethanolamine, propanolamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, methylethylamine, methyl Butylamine, propylamine, dipropylamine, tripropylamine, diisopropylamine, triisopropylamine, t-butylamine, 1,2-ethylenediamine, N, N, N ′, N′-tetra Amines such as til-1,2-ethylenediamine, di (n-butyl) amine, tributylamine, aniline, N-methylaniline, N, N-dimethylaniline, toluidine, N, N-dimethyltoluidine; acetaldehyde, butyraldehyde Aldehydes such as butanone, acetone, methyl propyl ketone, diethyl ketone; methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, propion Carboxylic acid esters such as methyl acid, γ-butyrolactone and butyl propionate; dimethyl ether, diethyl ether, methyl ethyl ether, dibutyl ether, diisopropyl ether, dioxane, trioxane, tetrahydrofuran , Ethers such as methyl-t-butyl ether and dimethoxyethane; heteroaromatic compounds such as furan, pyrrole, pyridine and thiophene; carboxamides such as formamide, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide and N-methylpyrrolidone Nitriles such as acetonitrile, propionitrile, butyronitrile; haloaromatic compounds such as chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, promobenzene; ethyl bromide, ethyl chloride, ethyl fluoride, Halogenated alkyl compounds such as butyl bromide, butyl chloride, methyl chloride, chloroform, dichloroethane, dichloromethane; nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, 1-nitro Tan, 2-nitrobutane, nitrobenzene, 2-nitrotoluene, nitro compounds such as 3-nitrotoluene and the like.
これらの中でも、エーテル類、ケトン類、エステル類、アルコール類が好ましい。
また、芳香族炭化水素溶媒の具体例としては、例えばベンゼン、トルエン、キシレン、エチルベンゼン、メシチレン、イソプロピルベンゼン等が挙げられる。これらの中でも、ベンゼン、トルエン、キシレンが好ましく、トルエンが特に好ましい。
かかる溶媒の使用量については、特に限定はされないが、粗ビニレンカーボネートに対して、通常、０．５〜２０重量倍、好ましくは０．７〜５重量倍、より好ましくは０．８〜３重量倍である。
Among these, ethers, ketones, esters, and alcohols are preferable.
Specific examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, mesitylene, isopropylbenzene, and the like. Among these, benzene, toluene and xylene are preferable, and toluene is particularly preferable.
The amount of the solvent used is not particularly limited, but is usually 0.5 to 20 times by weight, preferably 0.7 to 5 times by weight, more preferably 0.8 to 3 weights with respect to the crude vinylene carbonate. Is double.
晶析はビニレンカーボネートの約５〜７０重量％の溶液を放置して結晶を析出させてもよいが、その溶液を過冷却状態にすることにより結晶を析出させるのが好ましい。この場合、例えばその溶液を先ず０〜２０℃（温度Ａ）迄冷却し、温度Ａで約１〜２時間撹拌した後、更に温度Ａよりも５〜１５℃低い温度Ｂ迄、例えば０．１〜１０℃／時の速度で温度を下げ、この温度Ｂで約１〜２時間撹拌して晶析させるという手法が好ましい。 For crystallization, a solution of about 5 to 70% by weight of vinylene carbonate may be allowed to stand to precipitate crystals, but it is preferable to precipitate crystals by bringing the solution into a supercooled state. In this case, for example, the solution is first cooled to 0 to 20 ° C. (temperature A), stirred at temperature A for about 1 to 2 hours, and further to a temperature B lower than temperature A by 5 to 15 ° C., for example 0.1 A technique is preferred in which the temperature is lowered at a rate of 10 ° C./hour and the mixture is stirred at this temperature B for about 1 to 2 hours for crystallization.
なお、過冷却状態にして晶析を行う場合、その溶液に冷却された溶媒を添加するとか、ドライアイス等の低温を固体を投入する等して局所的な温度分布を作るとか、その溶液に脂肪族炭化水素のようなビニレンカーボネートの溶解度の小さい溶媒を添加するとか、液体又は固体のビニレンカーボネートを添加する等して局所的な濃度分布を作るとか、或いは種晶等を加えることも好ましい。 When crystallization is performed in a supercooled state, a local temperature distribution is created by adding a cooled solvent to the solution, or by introducing a solid at a low temperature such as dry ice, etc. It is also preferable to add a solvent having low solubility of vinylene carbonate such as an aliphatic hydrocarbon, create a local concentration distribution by adding liquid or solid vinylene carbonate, or add seed crystals.
結晶を更に析出又は成長させる方法としては、例えば冷却、脂肪族炭化水素のようなビニレンカーボネートの溶解度の小さい溶媒を添加する方法、冷却された溶媒を添加する方法、液体のビニレンカーボネートを添加する方法等やそれらの組合せによる方法が使用できる。
ビニレンカーボネートの回収率は使用する溶媒に対する溶解度に依存し、温度、溶媒量で任意に設定することが出来るが、通常ビニレンカーボネートの回収率が６０％以上、好ましくは８０％以上になるように設定される。
As a method for further precipitation or growth of crystals, for example, cooling, a method of adding a solvent having a low solubility of vinylene carbonate such as an aliphatic hydrocarbon, a method of adding a cooled solvent, a method of adding liquid vinylene carbonate Etc. or a combination thereof can be used.
The recovery rate of vinylene carbonate depends on the solubility in the solvent used, and can be arbitrarily set depending on the temperature and the amount of the solvent. Usually, the recovery rate of vinylene carbonate is set to 60% or more, preferably 80% or more. Is done.
析出した固体は、濾過、遠心分離等の方法で分離される。必要があれば、更に固体表面を適当な溶媒で洗浄する。この固体は、通常は融点以上に加熱し、ビニレンカーボネートを液体として取得する。このビニレンカーボネートはそのまま製品とすることもできるが、必要があればトッピング等で残留溶媒を除去することもできる。
このような方法により高純度のビニレンカーボネートを得ることができる。
The precipitated solid is separated by a method such as filtration or centrifugation. If necessary, the solid surface is further washed with a suitable solvent. This solid is usually heated above its melting point to obtain vinylene carbonate as a liquid. This vinylene carbonate can be used as a product as it is, but if necessary, the residual solvent can be removed by topping or the like.
High purity vinylene carbonate can be obtained by such a method.
但し、本発明にいう高純度ビニレンカーボネートとは、純度９９．５％以上、好ましくは９９．７％以上、より好ましくは９９．９％以上で、塩素化合物の含有量が全塩素量として５００ｐｐｍ以下、好ましくは２００ｐｐｍ以下、より好ましくは５０ｐｐｍ以下のものを指す。
なお、この方法でも充分な品質のビニレンカーボネートが得られるが、更に高品質なものが必要である場合には本発明の方法を繰り返して使用することが出来る。
However, the high-purity vinylene carbonate referred to in the present invention means a purity of 99.5% or more, preferably 99.7% or more, more preferably 99.9% or more, and the chlorine compound content is 500 ppm or less as the total chlorine content. , Preferably 200 ppm or less, more preferably 50 ppm or less.
This method can also obtain a vinylene carbonate having a sufficient quality. However, when a higher quality vinylene carbonate is required, the method of the present invention can be used repeatedly.
以下、実施例により、本発明を更に具体的に説明するが、本発明は、その要旨を越えない限りこれらの実施例に限定されるものではない。
なお、分析はガスクロマトグラフィーで実施した。純度は溶媒が残存している場合は溶媒をカットした数値を使用した。
純度＝（ビニレンカーボネート面積）／（全面積−残留溶媒ピーク面積）
実施例１〜１０
撹拌機能を備えた５００ｍｌの四つ口フラスコに、ビニレンカーボネート（ＶＣ）と溶媒を仕込み、撹拌しながら、１時間当り２℃の速度で冷却した。ある温度（温度Ａ）まで冷却すると固体が析出するので、その温度で１時間撹拌した後、所定の温度（温度Ｂ）まで１時間当り２℃の速度で冷却し、更に１時間撹拌した。固体を濾別し、５℃のヘキサンで２回洗浄した後、加熱融解し、液体を回収した。以下の表１に結果を示した。
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded.
The analysis was performed by gas chromatography. For the purity, when the solvent remained, a value obtained by cutting the solvent was used.
Purity = (Vinylene carbonate area) / (Total area−Residual solvent peak area)
Examples 1-10
A 500 ml four-necked flask equipped with a stirring function was charged with vinylene carbonate (VC) and a solvent, and cooled at a rate of 2 ° C. per hour while stirring. Solids precipitated when cooled to a certain temperature (temperature A). After stirring at that temperature for 1 hour, the mixture was cooled to a predetermined temperature (temperature B) at a rate of 2 ° C. per hour and further stirred for 1 hour. The solid was separated by filtration, washed twice with hexane at 5 ° C., and then melted by heating to recover the liquid. The results are shown in Table 1 below.
実施例１１、１２
撹拌機能を備えた５０ｍｌの三つ口フラスコに、ビニレンカーボネート（純度９９．２４％、全塩素６２７０ｐｐｍ）１０ｇ、溶媒１０ｇを仕込み、撹拌しながら冷却したところ固体が析出した。５℃で１時間撹拌した後、撹拌を停止し、−５℃で１２時間静置した。固体を濾別し、５℃のヘキサンで２回洗浄した後、加熱融解し、液体を回収した。結果を以下の表２に示した。
Examples 11 and 12
A 50 ml three-necked flask equipped with a stirring function was charged with 10 g of vinylene carbonate (purity 99.24%, total chlorine 6270 ppm) and 10 g of solvent, and cooled with stirring to precipitate a solid. After stirring at 5 ° C for 1 hour, stirring was stopped and the mixture was allowed to stand at -5 ° C for 12 hours. The solid was separated by filtration, washed twice with hexane at 5 ° C., and then melted by heating to recover the liquid. The results are shown in Table 2 below.
実施例１３
撹拌機能を備えた２５０Ｌ反応器に、ビニレンカーボネート（純度９８．６９％、全塩素３１６０ｐｐｍ）４０．０ｋｇとトルエン４０．０ｋｇ、ヘキサン４０．０ｋｇを仕込み撹拌しながら冷却した。１４．７℃で種晶４０ｇを添加し３０分撹拌した後、１４．３〜５℃で６時間撹拌し、更に４時間かけて４．０℃まで冷却した。固体を濾別し、５℃のヘキサン４０ｋｇで２回洗浄し、ＶＣを固体で得た。回収率９３．２％、純度９９．９４％、全塩素１１ｐｐｍ。
Example 13
A 250 L reactor equipped with a stirring function was charged with 40.0 kg of vinylene carbonate (purity 98.69%, total chlorine 3160 ppm), 40.0 kg of toluene, and 40.0 kg of hexane, and cooled while stirring. After adding 40 g of seed crystals at 14.7 ° C. and stirring for 30 minutes, the mixture was stirred at 14.3 to 5 ° C. for 6 hours, and further cooled to 4.0 ° C. over 4 hours. The solid was filtered off and washed twice with 40 kg of hexane at 5 ° C. to obtain VC as a solid. Recovery rate 93.2%, purity 99.94%, total chlorine 11ppm.
実施例１４
掻き取り翼付きの２５０Ｌ反応器に、ビニレンカーボネート（純度９８．６９％、全塩素３１６０ｐｐｍ）５０．０ｋｇとトルエン５０．０ｋｇ、ヘキサン５０．０ｋｇを仕込み撹拌しながら冷却した。１４．７℃で種晶５０ｇを添加し３０分撹拌した後、２．５時間かけて４．０℃まで冷却した。固体を濾別し、５℃のヘキサン５０ｋｇで２回洗浄し、ＶＣを固体で得た。回収率９３．３％、純度９９．９４％、全塩素１５ｐｐｍ。
Example 14
A 250 L reactor equipped with a scraping blade was charged with 50.0 kg of vinylene carbonate (purity 98.69%, total chlorine 3160 ppm), 50.0 kg of toluene, and 50.0 kg of hexane, and cooled with stirring. After adding 50 g of seed crystals at 14.7 ° C. and stirring for 30 minutes, the mixture was cooled to 4.0 ° C. over 2.5 hours. The solid was filtered off and washed twice with 50 kg of hexane at 5 ° C. to obtain VC as a solid. Recovery rate 93.3%, purity 99.94%, total chlorine 15ppm.
比較例１
ビニレンカーボネート１００ｇ（純度９９．２４％、全塩素６２７０ｐｐｍ）を４段の蒸留塔を使用し、還流比５〜１０で２回精密蒸留した。収率６９％、純度９９．８０％、全塩素量５３０ｐｐｍ。
Comparative Example 1
100 g of vinylene carbonate (purity 99.24%, total chlorine 6270 ppm) was subjected to precision distillation twice using a four-stage distillation column at a reflux ratio of 5 to 10. Yield 69%, purity 99.80%, total chlorine content 530 ppm.
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| KR20170030523A (en) | 2014-07-14 | 2017-03-17 | 우베 고산 가부시키가이샤 | High-purity vinylene carbonate, nonaqueous electrolytic solution, and electricity storage device including same |
| TWI664769B (en) | 2017-03-17 | 2019-07-01 | 日商旭化成股份有限公司 | Non-aqueous electrolyte, non-aqueous secondary battery, unit pack and merger system |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US3457279A (en) * | 1964-10-21 | 1969-07-22 | Jefferson Chem Co Inc | Vinylene carbonate production |
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| JP3368832B2 (en) * | 1998-07-10 | 2003-01-20 | 宇部興産株式会社 | Method for producing vinylene carbonate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3457279A (en) * | 1964-10-21 | 1969-07-22 | Jefferson Chem Co Inc | Vinylene carbonate production |
| JP2000138071A (en) * | 1998-08-27 | 2000-05-16 | Ube Ind Ltd | Nonaqueous electrolyte, and lithium secondary battery using the same |
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