JP4722327B2 - Method for producing acetylenic diol compound - Google Patents

Description

（式中、Ｒ¹及びＲ²は、炭素数１〜１２のアルキル基、アラルキル基、アリール基又はアルカリール基を示す。）で表される脂肪族ケトン類又は芳香族ケトン類、或いは、下記の一般式（ＩＩ）
【化２】

（式中、Ｒ³は炭素数５〜１２のアルキレン基を示す。）で表される環状ケトン類である。
【００１５】
一般式（Ｉ）で表されるケトン類の具体例としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、２−へキサノン、２−オクタノン、アセトフェノン、エチルフェニルケトン、エチルトリルケトン等を、又、一般式（ＩＩ）で表されるケトン類の具体例としては、シクロペンタノン、シクロへキサノン、メチルシクロへキサノン等をそれぞれ挙げることができる。
【００１６】
上記ケトン類の使用量については、特に制限はないが、一般には使用する溶媒（後述する）に対して５〜６０重量％の範囲である。
【００１７】
本発明では、上記ケトン類とアセチレンとを、アルカリ触媒の存在下に反応させるのであるが、ここで用いられるアルカリ触媒としては、アルカリ金属、アルカリ金属水酸化物或いはアルカリ金属アルコラートから選択することができる。
【００１８】
上記アルカリ触媒のうち、アルカリ金属としては、例えば金属ナトリウムや金属カリウムが挙げられ、又、アルカリ金属水酸化物としては、例えば水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化ルビジウムや水酸化セシウムが挙げられ、更に、アルカリ金属アルコラートとしては、例えばカリウムメチラート、カリウムエチラート、カリウムイソブチラート、カリウムーｔ−ブチラート、ナトリウムメチラート、ナトリウムエチラート等の脂肪族系アルカリ金属アルコラートが挙げられ、又、カリウムシクロヘキシラート等の脂環式アルカリ金属アルコラートも使用することができる。
【００１９】
尚、上記のアルカリ触媒は、原料のケトン類１モルに対して０．１乃至２０モル、好ましくは０．５乃至１０モルの割合で使用される。
【００２０】
又、本発明の製造方法における反応溶媒としては、後述する抽出剤である非プロトン性極性溶媒若しくはメタノールと相溶しにくく、層分離しやすい点から、鎖状又は環状の脂肪族炭化水素を使用するのであり、この内の鎖状脂肪族炭化水素としては、例えばヘキサン、ヘプタン、オクタン、ノナン、デカン等の飽和炭化水素；ジイソブチレン、トリイソブチレン、テトライソブチレン等の不飽和炭化水素を使用することができ、又、環状脂肪族炭化水素（脂環式炭化水素）としては、シクロヘキサン、メチルシクロヘキサン、デカリン等を使用することができる。
【００２１】
更に、これらの鎖状脂肪族炭化水素同士の混合物や、環状脂肪族炭化水素同士の混合物或いは鎖状脂肪族炭化水素と環状脂肪族炭化水素との混合物（いわゆるナフテン系溶媒）も、本発明の製造方法における反応溶媒として使用することができる。
【００２２】
尚、ＡＤＯの製造自体には、芳香族炭化水素や脂肪族エーテル等も使用できるが、本発明で使用する抽出剤と比較的相溶性がよく、層分離しにくいために好ましくない。
【００２３】
本発明によるＡＤＯの製造は、連続式でもバッチ式でも可能であり、バッチ式の場合、反応器にまず反応溶媒としての脂肪族炭化水素溶媒、アルカリ触媒を供給し、次いでアセチレンを導入し、更にケトン類を供給した後、攪拌加熱して反応させる。又、連続式の場合、バッチ式と同様に反応をスタートさせた後、各原料を連続的に供給すると共に、反応系の液面を一定に保ちながら生成混合物を連続的に抜き出す。尚、このときの反応温度は０℃乃至１００℃、好ましくは１０℃乃至６０℃である。
【００２４】
反応圧力は、アセチレン分圧として通常０〜１ＭＰａ（ゲージ圧）、好ましくは０〜０．２ＭＰａ（ゲージ圧）であり、アセチレン分圧が高ければ高いほど反応速度が大きくなるが、アセチレンは分解爆発を起こしやすいので、それを防止するためにはできるだけアセチレン分圧を低くすることが好ましい。尚、分解爆発を防止するために窒素、アルゴン、プロパン等の不活性ガスを導入し、アセチレンを希釈して反応させてもよい。
【００２５】
反応時間は、反応温度やアセチレン分圧等のその他の条件に依るが、バッチ式の場合、通常０．５〜２０時間、好ましくは１〜８時間である。
【００２６】
上記説明した反応により、一般式（Ｉ）のケトン類を使用した場合、主として下記の一般式（ＩＩＩ）
【化３】

（式中、Ｒ¹及びＲ²は前記と同じ基を示す。）で表されるＡＤＯが、又、一般式（ＩＩ）のケトン類を使用した場合、主として下記の一般式（ＩＶ）
【化４】

（式中、Ｒ³は前記と同じ基を示す。）で表されるＡＤＯが生成し、その際、通常は少量のＡＭＯも副生する。
【００２７】
又、その他に、前記のとおりアルドール縮合による副生物として、例えば一般式（Ｉ）のケトン類を使用した場合には、主に下記の一般式（Ｖ）
【化５】

（式中、Ｒ¹及びＲ²は前記と同じ基を、Ｒ⁴はＲ¹に由来するアルキレン基を示す。）で表される縮合２量体、或いは、主に下記の一般式（ＶＩ）
【化６】

（式中、Ｒ¹及びＲ²は前記と同じ基を、Ｒ⁵はＲ²に由来するアルキレン基を、Ｒ⁶はＲ¹に由来する水素原子又はアルキル基をそれぞれ示す。）で表される縮合３量体等のケトン縮合体が、通常１，０００〜１０，０００ｐｐｍ副生する。
【００２８】
反応終了後に上記のような成分を含む反応混合物からは、通常まず、その中のアルカリ触媒を除去し、続いてケトン縮合体を分離することにより、少量のＡＭＯを含むＡＤＯを得る。
【００２９】
アルカリ触媒の除去は、一般に反応混合物に水を加えてアルカリ触媒を抽出分離すればよいが、場合により、有機相に微量に残存するアルカリ触媒を、更に無機酸或いは有機酸で中和して除去することもできる。
【００３０】
又、ケトン縮合体の分離は、上記の水層分離後の反応混合物（有機層）に、本発明で抽出剤として使用する非プロトン性極性溶媒或いはメタノールを加え、抽出することにより行う。即ち、得られた有機層に抽出剤を加えると、反応溶媒層である上層と抽出剤層である下層の２つの層に分離し、下層の抽出剤層には大部分のＡＤＯが袖出され、上層の反応溶媒層にはケトン縮合体が抽出される。
【００３１】
このようにして得られた下層、即ち主としてＡＤＯ、ＡＭＯ及び抽出剤からなる混合液からは、蒸留により通常は低沸点である抽出剤を留去して除去し、次いでＡＤＯとＡＭＯからなる残液を蒸留することにより、沸点に差のあるＡＤＯとＡＭＯとを分離して、容易にＡＤＯを得ることができるのである。
【００３２】
本発明における抽出剤としては、上記の通り非プロトン性極性溶媒又はメタノールが用いられ、これらの内の非プロトン性極性溶媒の具体例としては、ジメチルスルホキシド、ジエチルスルホキシド、テトラメチレンスルホキシド、アセトニトリル、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジエチルアセ卜アミド、Ｎ−メチル−２−ピロリドン、Ｎ−ビニル−２−ピロリドン、１，３−ジメチル−２−イミダゾリジノン、１，３，４−トリメチル−２−イミダゾリジノン、１，３−ジエチル−２−イミダゾリジノン、１，３−ジプロピル−２−イミダゾリジノン、ジメチルプロピレンウレア、テトラメチルウレア等を挙げることができる。
【００３３】
中でも上記ジメチルスルホキシド、テトラメチレンスルホキシド、アセトニトリル、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチル−２−ピロリドン、１，３−ジメチル−２−イミダゾリジノンは、相対的にＡＤＯの抽出能力が高い上に、脂肪族炭化水素溶媒と相溶しにくく、分液する時の分離性がよいので好ましい。
【００３４】
又、上記非プロトン性極性溶媒の他、メタノールも本発明で使用するための抽出剤としての適性に優れるが、メタノールの代わりにエタノールやその他のアルコールを使用した場合、本発明で用いられる反応溶媒と比較的相溶し易く、分液する時の分離性がよくないことが確認されている。
【００３５】
尚、本発明における抽出剤の使用量は、ＡＤＯの容量に対して０．１乃至２０倍容量、好ましくは０．５乃至１０倍容量である。
【００３６】
上記抽出剤による抽出方法は、バッチ式でも連続式でも可能であり、バッチ式の場合、非プロトン性極性溶媒、ＡＤＯ、ケトン縮合体等を含む反応混合物に抽出剤を添加し、充分に混合、次いで静置した後分液する。抽出時間は１分以上、好ましくは３〜６０分で、抽出操作後の静置時間は１分以上、好ましくは３〜６０分である。
【００３７】
抽出剤層中のケトン縮合体の濃度が高いときには、一度抽出処理して回収した抽出剤層に純粋の反応溶媒（脂肪族炭化水素）を再度添加し、抽出操作を繰り返せばよく、反応原料として前記ケトン類を使用した場合、一般に反応後の反応混合物中のケトン縮合体の濃度は約０．１〜３％の範囲であり、その濃度にもよるが抽出操作は２回乃至５回で充分である。
【００３８】
次に、回収した抽出剤層を減圧蒸留に付し、抽出剤を留去することにより、少量のＡＭＯを含む粗ＡＤＯを得ることができるので、最後に、この粗ＡＤＯを減圧蒸留してＡＭＯを分離除去することにより、通常、ケトン縮合体の濃度が数百ｐｐｍ以下の高純度なＡＤＯを製造することができる。
【００３９】
【実施例】
以下、実施例により本発明を更に詳細に説明するが、本発明はこれに限定されるものではない。
【００４０】
実施例１
１）ケトンとアセチレンの反応
１Ｌのオートクレーブに、水酸化カリウム粉末（純度９５％）４７．５ｇ及びナフテン系溶媒（沸点範囲２１０〜２３０℃、比重０．７９）４００ｇを仕込み、アセチレンを圧力０．０２ＭＰａ（ゲージ圧）まで導入した。更に、原料ケトンとしてメチルイソブチルケトン５０ｇを導入した。攪拌しながら反応させ、反応熱を除去することにより、温度を２５℃に保持した。２時間反応した後、反応混合物をガスクロマトグラフィーにより分析すると、ＡＤＯとして２，４，７，９−テトラメチル−５−デシンー４，７−ジオールが９．０ｗｔ％、ＡＭＯとして３，５−ジメチル−１−ヘキシン−３−オールが２．０ｗｔ％、ケトン縮合体２．６ｗｔ％が含まれていた。得られた反応液５００ｇを分液ロートに移し、これに水を加えて振とうすることにより、仕込みの水酸化カリウムの９７ｗｔ％を抽出、除去した。次いで有機相のみを分離し、これに濃度０．１ｍｏｌ／Ｌの塩酸を加えて微量に残留する水酸化カリウムを中和、除去し、４５６ｇの有機層を回収した。
【００４１】
２）抽出操作
上記の有機相４５６ｇを分液ロートに採り、抽出剤としてジメチルスルホキシド９０ｇを加え、充分に振とうした後、５分間静置した。次に、下層部１５１ｇを回収し、反応に用いたナフテン系溶媒３６３ｇを加え、再度充分に振とうし、５分間静置をした。２層に分離した上層及び下層をガスクロマトグラフィーにより分析したところ、ＡＤＯの上層／下層濃度比は１／２９．６（ｗｔ％／ｗｔ％）で、ＡＤＯの９０ｗｔ％以上が下層に抽出されていた。尚、下層部にはケトン縮合体が１６ｐｐｍの濃度で含まれていた。
【００４２】
３）抽出剤及びＡＭＯの分離
上記下層部１４０ｇを理論段数８段のディクソン型充填物を充填した蒸留塔に供給し、減圧蒸留した。即ち、減圧度１２ｍｍＨｇ、塔頂温度数十度の条件下で、まずＡＭＯが流出し、次いで抽出剤が留出した。最後に、塔頂温度１４８℃で留出する留分を回収した。この留分は、分析の結果、ケトン縮合体濃度７７ｐｐｍの高純度ＡＤＯであった。
【００４３】
比較例１
実施例１において触媒除去処理を行った有機層について、抽出剤による抽出処理の代わりに蒸留を行った。即ち、有機相１９６３ｇを理論段数８段のディクソン型充填物を充填した蒸留塔に供給し、塔頂温度１４８℃、蒸留釜１５１℃、減圧度１２ｍｍＨｇの条件下で減圧蒸留した。主にＡＤＯからなる留出液６５７ｇが得られ、その中のケトン縮合体の濃度は１３６６ｐｐｍであり、ＡＤＯ（即ち、２，４，７，９−テトラメチル−５−デシン−４，７−ジオール）の純度は９９．８％であった。従って、実施例１に比べＡＤＯ中のケトン縮合体含量が多く、本発明の製造方法に比べてケトン縮合体の分離効果は劣っていた。
【００４４】
実施例２
１）抽出操作
分液ロートに、実施例１と同様に触媒を抽出処理して得られた有機層３００ｇを採取し、抽出剤としてＮ−メチル−２−ピロリドン２８．７ｇを加えた。次いで分液ロートを充分振とうした後、５分間静置した。下層部３６ｇを回収し、新たなナフテン系溶媒３０Ｏｇを添加して、再度振とうした後、静置した。２層に分離した上層及び下層を分析したところ、ＡＤＯの上層／下層濃度比が１／８．６（ｗｔ％／ｗｔ％）であった。尚、下層部のケトン縮合体濃度は９８ｐｐｍであった
【００４５】
２）抽出剤及びAＭＯの分離
上記下層部について、実施例１と同じ条件で蒸留し、抽出剤及びＡＭＯを分離したところ、ケトン縮合体の濃度が５４３ｐｐｍの高純度ＡＤＯが得られた。
【００４６】
実施例３〜５
抽出剤の種類を表１のとおり変化させた以外は、実施例２と同様に抽出実験を行った。抽出条件及び結果を表１にまとめて示す。
【００４７】
【表１】

【００４８】
【発明の効果】
上記実施例及び比較例から明らかなように、本発明のアセチレンジオールの製造方法によれば、特定の反応溶媒と反応混合物の抽出剤とを組み合わせることにより、副生するケトン縮合体を効率的に分離することができ、高純度のアセチレンジオール化合物を得ることができる。
【００４９】
又、本発明のアセチレンジオールの製造方法は、反応溶媒及び抽出剤のロスも少ないという優れたものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing an acetylenic diol compound, and more specifically, a high-purity acetylenic diol compound is obtained by removing a by-product from a reaction mixture containing an acetylenic diol compound obtained by reacting a ketone with acetylene. The present invention relates to a method for producing an acetylenic diol compound that can be obtained.
[0002]
[Prior art]
Conventionally, for example, acetylenic diol compounds represented by the following general formulas (III) and (IV) (hereinafter sometimes abbreviated as ADO) are generally ketones in the presence of an alkali catalyst such as potassium hydroxide. It is produced by reacting 2 moles with 1 mole of acetylene (see, for example, U.S. Pat. Nos. 2,385,546 and 2,455,058). As a result, an acetylene monool compound (hereinafter sometimes abbreviated as AMO), which is a compound in which 1 mol of ketones and 1 mol of acetylene are generally reacted, is by-produced.
[0003]
In addition, it is known that ketones that are raw materials for the above reaction generally cause a so-called aldol condensation reaction in the presence of an alkali catalyst. In combination with AMO, it is a major cause of the decrease in ADO purity.
[0004]
By the way, ADO has a triple bond with high electron density and two hydroxyl groups adjacent to it, and these groups act synergistically as a highly polar group like no other. Derivatives exhibit properties such as strong orientation to metals, antifoaming properties, and wettability, and are used as nonionic surfactants, metal surface treatment agents, pharmaceutical raw materials, and the like.
[0005]
However, even if a relatively small amount of ketone condensate produced as a by-product in the production of ADO is mixed, the above effect is weakened, and in some applications, the content of the ketone condensate. Therefore, it is essential to remove the ketone condensate from the ADO.
[0006]
Therefore, the technology for producing a purified ADO by removing the ketone condensate from the reaction product containing ADO has been repeatedly developed. The ketone condensate, particularly the dimer or the trimer, has a boiling point with ADO. Therefore, in order to separate and remove the ketone condensate to several hundred ppm or less by the distillation method, it is necessary to increase the number of stages of the distillation column from several stages to 10 stages in the usual case. However, it is not necessarily advantageous from the viewpoint of productivity and energy efficiency.
[0007]
The AMO produced as a by-product can be separated by a general means such as distillation because of the large difference in boiling point from ADO.
[0008]
[Problems to be solved by the invention]
Accordingly, the object of the present invention is to eliminate the above-mentioned problems of the prior art and to efficiently produce a by-product ketone condensate in the production of ADO by reacting ketones and acetylene in the presence of an alkali catalyst. An object of the present invention is to provide a method capable of producing high-purity ADO by separating and removing automatically.
[0009]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have used a specific solvent for the synthesis reaction of ADO, and combined it with a specific extractant to efficiently perform the ketone condensate. It was found that acetylene diol compounds can be produced with high purity, and the present invention was completed.
[0010]
That is, the gist of the present invention is to use an aliphatic hydrocarbon as a reaction solvent and a produced acetylenic diol compound in a method for producing an acetylenic diol compound by reacting a ketone with acetylene in the presence of an alkali catalyst. The reaction mixture is extracted with an aprotic polar solvent or an extraction agent composed of methanol to obtain an acetylenediol compound.
[0011]
In the method for producing an acetylenic diol compound combining a predetermined reaction solvent and a predetermined extractant, which is a feature of the present invention, the reaction solvent is preferentially used as a by-product ketone condensate in the reaction mixture containing ADO. On the other hand, the produced ADO has low solubility, and the extractant preferentially dissolves ADO in the reaction mixture, while the ketone condensate has low solubility.
[0012]
As a result, the ketone condensate by-produced in the reaction mixture can be separated and removed efficiently, and the reaction solvent and the extractant are difficult to dissolve each other, so that the layers are easily separated, and each loss is very small. It makes it possible to produce acetylenic diol compounds under favorable conditions.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
[0014]
In the present invention, one of the main raw materials used for the production of ADO is ketones, and the following general formula (I)
[Chemical 1]

(Wherein R ¹ and R ² represent an alkyl group having 1 to 12 carbon atoms, an aralkyl group, an aryl group, or an alkaryl group), or the following: General formula (II)
[Chemical 2]

(Wherein R ³ represents an alkylene group having 5 to 12 carbon atoms).
[0015]
Specific examples of the ketones represented by the general formula (I) include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, 2-octanone, acetophenone, ethyl phenyl ketone, ethyl tolyl ketone, and the like. Specific examples of the ketones represented by (II) include cyclopentanone, cyclohexanone, methylcyclohexanone and the like.
[0016]
Although there is no restriction | limiting in particular about the usage-amount of the said ketones, Generally it is the range of 5-60 weight% with respect to the solvent (after-mentioned) to be used.
[0017]
In the present invention, the ketones and acetylene are reacted in the presence of an alkali catalyst. The alkali catalyst used here may be selected from alkali metals, alkali metal hydroxides or alkali metal alcoholates. it can.
[0018]
Among the alkali catalysts, examples of the alkali metal include metal sodium and metal potassium, and examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide and hydroxide. In addition, examples of the alkali metal alcoholate include aliphatic alkali metal alcoholates such as potassium methylate, potassium ethylate, potassium isobutyrate, potassium-t-butyrate, sodium methylate, and sodium ethylate. Moreover, alicyclic alkali metal alcoholates such as potassium cyclohexylate can also be used.
[0019]
The alkali catalyst is used in a proportion of 0.1 to 20 mol, preferably 0.5 to 10 mol, per 1 mol of the starting ketones.
[0020]
In addition, as the reaction solvent in the production method of the present invention, a chain or cyclic aliphatic hydrocarbon is used because it is not compatible with an aprotic polar solvent or methanol as an extractant described later and is easily separated into layers. Of these, as the chain aliphatic hydrocarbons, for example, saturated hydrocarbons such as hexane, heptane, octane, nonane and decane; and unsaturated hydrocarbons such as diisobutylene, triisobutylene and tetraisobutylene should be used. In addition, as the cycloaliphatic hydrocarbon (alicyclic hydrocarbon), cyclohexane, methylcyclohexane, decalin and the like can be used.
[0021]
Furthermore, a mixture of these chain aliphatic hydrocarbons, a mixture of cycloaliphatic hydrocarbons, or a mixture of chain aliphatic hydrocarbons and cycloaliphatic hydrocarbons (so-called naphthenic solvents) is also included in the present invention. It can be used as a reaction solvent in the production method.
[0022]
In addition, although aromatic hydrocarbon, aliphatic ether, etc. can be used for manufacture of ADO itself, since it is relatively compatible with the extractant used in the present invention and is difficult to separate, it is not preferable.
[0023]
The ADO according to the present invention can be produced continuously or batchwise. In the case of the batch method, an aliphatic hydrocarbon solvent as a reaction solvent and an alkali catalyst are first supplied to the reactor, and then acetylene is introduced. After supplying the ketones, the reaction is carried out by stirring and heating. In the case of the continuous type, after starting the reaction as in the case of the batch type, each raw material is continuously supplied, and the product mixture is continuously extracted while keeping the liquid level of the reaction system constant. The reaction temperature at this time is 0 ° C. to 100 ° C., preferably 10 ° C. to 60 ° C.
[0024]
The reaction pressure is usually 0 to 1 MPa (gauge pressure), preferably 0 to 0.2 MPa (gauge pressure) as the acetylene partial pressure, and the higher the acetylene partial pressure, the higher the reaction rate, but acetylene decomposes and explodes. In order to prevent this, it is preferable to reduce the acetylene partial pressure as much as possible. In order to prevent decomposition and explosion, an inert gas such as nitrogen, argon or propane may be introduced to dilute the acetylene for reaction.
[0025]
The reaction time depends on other conditions such as reaction temperature and acetylene partial pressure, but in the case of a batch system, it is usually 0.5 to 20 hours, preferably 1 to 8 hours.
[0026]
When the ketone of the general formula (I) is used by the reaction described above, the following general formula (III)
[Chemical 3]

(In the formula, R ¹ and R ² represent the same groups as described above.) When the ADO represented by the general formula (II) is used, the following general formula (IV) is mainly used.
[Formula 4]

(Wherein R ³ represents the same group as described above) is produced, and a small amount of AMO is usually produced as a by-product.
[0027]
In addition, as described above, when, for example, a ketone of the general formula (I) is used as a by-product by aldol condensation, the following general formula (V)
[Chemical formula 5]

(Wherein R ¹ and R ² represent the same groups as described above, and R ⁴ represents an alkylene group derived from R ¹ ), or mainly represented by the following general formula (VI)
[Chemical 6]

(Wherein R ¹ and R ² represent the same groups as described above, R ⁵ represents an alkylene group derived from R ² , and R ⁶ represents a hydrogen atom or an alkyl group derived from R ¹ ). A ketone condensate such as a condensation trimer is usually produced as a by-product of 1,000 to 10,000 ppm.
[0028]
From the reaction mixture containing the above components after completion of the reaction, usually, the alkali catalyst therein is first removed, and then the ketone condensate is separated to obtain ADO containing a small amount of AMO.
[0029]
In general, the alkali catalyst can be removed by adding water to the reaction mixture and extracting and separating the alkali catalyst. In some cases, the alkali catalyst remaining in a trace amount in the organic phase is further neutralized with an inorganic acid or an organic acid and removed. You can also
[0030]
Separation of the ketone condensate is performed by adding the aprotic polar solvent or methanol used as an extractant in the present invention to the reaction mixture (organic layer) after the aqueous layer separation described above and extracting it. That is, when an extractant is added to the obtained organic layer, it is separated into two layers, an upper layer which is a reaction solvent layer and a lower layer which is an extractant layer, and most of the ADO is exposed in the lower extractant layer. The ketone condensate is extracted in the upper reaction solvent layer.
[0031]
From the lower layer thus obtained, that is, a mixed solution mainly composed of ADO, AMO and an extractant, the extractant usually having a low boiling point is removed by distillation to remove it, and then a residual liquid composed of ADO and AMO is removed. Is distilled to separate ADO and AMO having different boiling points, so that ADO can be easily obtained.
[0032]
As the extractant in the present invention, an aprotic polar solvent or methanol is used as described above. Specific examples of the aprotic polar solvent include dimethyl sulfoxide, diethyl sulfoxide, tetramethylene sulfoxide, acetonitrile, N , N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 1,3-dimethyl- 2-imidazolidinone, 1,3,4-trimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone, dimethylpropylene urea, tetramethyl Examples include urea.
[0033]
Among them, the above dimethyl sulfoxide, tetramethylene sulfoxide, acetonitrile, N, N-dimethylformamide, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone have relatively high ADO extraction ability. It is preferable because it is hardly compatible with an aliphatic hydrocarbon solvent and has good separation properties when it is separated.
[0034]
In addition to the above aprotic polar solvent, methanol is also excellent in suitability as an extractant for use in the present invention, but when ethanol or other alcohol is used instead of methanol, the reaction solvent used in the present invention It has been confirmed that they are relatively compatible with each other and have poor separation properties when separated.
[0035]
In addition, the usage-amount of the extractant in this invention is 0.1 thru | or 20 times capacity | capacitance with respect to the capacity | capacitance of ADO, Preferably it is 0.5 thru | or 10 times capacity.
[0036]
The extraction method using the above extractant can be either a batch type or a continuous type. In the case of the batch type, the extractant is added to a reaction mixture containing an aprotic polar solvent, ADO, a ketone condensate, etc., and mixed thoroughly. Then, after standing, liquid separation is performed. The extraction time is 1 minute or longer, preferably 3 to 60 minutes, and the standing time after the extraction operation is 1 minute or longer, preferably 3 to 60 minutes.
[0037]
When the concentration of the ketone condensate in the extractant layer is high, pure reaction solvent (aliphatic hydrocarbon) may be added again to the extractant layer that has been extracted and recovered once, and the extraction operation may be repeated. When the ketones are used, the concentration of the ketone condensate in the reaction mixture after the reaction is generally in the range of about 0.1 to 3%. Depending on the concentration, the extraction operation may be performed 2 to 5 times. It is.
[0038]
Next, since the recovered extractant layer is subjected to vacuum distillation and the extractant is distilled off, crude ADO containing a small amount of AMO can be obtained. Finally, this crude ADO is distilled under reduced pressure to give AMO. By separating and removing, usually, high-purity ADO having a ketone condensate concentration of several hundred ppm or less can be produced.
[0039]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this.
[0040]
Example 1
1) Reaction of ketone and acetylene A 1 L autoclave was charged with 47.5 g of potassium hydroxide powder (purity 95%) and 400 g of a naphthenic solvent (boiling range 210-230 ° C., specific gravity 0.79), and acetylene was added at a pressure of 0. The pressure was introduced up to 02 MPa (gauge pressure). Further, 50 g of methyl isobutyl ketone was introduced as a raw material ketone. The temperature was kept at 25 ° C. by reacting with stirring and removing heat of reaction. After reacting for 2 hours, the reaction mixture was analyzed by gas chromatography, and 9.0 wt% of 2,4,7,9-tetramethyl-5-decyne-4,7-diol as ADO and 3,5-dimethyl as AMO. The amount of -1-hexyn-3-ol was 2.0 wt% and the ketone condensate was 2.6 wt%. 500 g of the obtained reaction solution was transferred to a separatory funnel, and water was added to this and shaken to extract and remove 97 wt% of the charged potassium hydroxide. Subsequently, only the organic phase was separated, and 0.1 mol / L hydrochloric acid was added thereto to neutralize and remove the trace amount of potassium hydroxide, and 456 g of the organic layer was recovered.
[0041]
2) Extraction operation 456 g of the above organic phase was placed in a separating funnel, 90 g of dimethyl sulfoxide was added as an extractant, and the mixture was shaken sufficiently, and then allowed to stand for 5 minutes. Next, 151 g of the lower layer part was recovered, 363 g of the naphthenic solvent used in the reaction was added, and the mixture was shaken sufficiently again and allowed to stand for 5 minutes. When the upper and lower layers separated into two layers were analyzed by gas chromatography, the ADO upper layer / lower layer concentration ratio was 1 / 29.6 (wt% / wt%), and 90 wt% or more of ADO was extracted to the lower layer. It was. The lower layer portion contained a ketone condensate at a concentration of 16 ppm.
[0042]
3) Separation of extractant and AMO 140 g of the lower layer was supplied to a distillation column packed with a Dixon-type packing having 8 theoretical plates and distilled under reduced pressure. That is, under the conditions of a reduced pressure of 12 mmHg and a tower top temperature of several tens of degrees, AMO first flowed out, and then the extractant distilled out. Finally, a fraction distilled at a tower top temperature of 148 ° C. was recovered. As a result of analysis, this fraction was high-purity ADO having a ketone condensate concentration of 77 ppm.
[0043]
Comparative Example 1
About the organic layer which performed the catalyst removal process in Example 1, it distilled instead of the extraction process by an extracting agent. That is, 1963 g of the organic phase was supplied to a distillation column packed with a Dixon-type packing having 8 theoretical plates, and distilled under reduced pressure under the conditions of a column top temperature of 148 ° C., a distillation kettle of 151 ° C., and a degree of vacuum of 12 mmHg. 657 g of a distillate mainly composed of ADO is obtained, and the concentration of the ketone condensate therein is 1366 ppm, and ADO (that is, 2,4,7,9-tetramethyl-5-decyne-4,7-diol) ) Was 99.8%. Therefore, the content of the ketone condensate in ADO was larger than that in Example 1, and the separation effect of the ketone condensate was inferior compared with the production method of the present invention.
[0044]
Example 2
1) 300 g of an organic layer obtained by extracting the catalyst in the same manner as in Example 1 was collected in an extraction operation separatory funnel, and 28.7 g of N-methyl-2-pyrrolidone was added as an extractant. Next, the separatory funnel was sufficiently shaken and allowed to stand for 5 minutes. The lower layer part 36g was collect | recovered, the new naphthenic solvent 30Og was added, and it left still, after shaking again. When the upper layer and the lower layer separated into two layers were analyzed, the ADO upper layer / lower layer concentration ratio was 1 / 8.6 (wt% / wt%). The ketone condensate concentration in the lower layer was 98 ppm.
2) Separation of extractant and AMO The lower layer was distilled under the same conditions as in Example 1 to separate the extractant and AMO. As a result, high-purity ADO having a ketone condensate concentration of 543 ppm was obtained.
[0046]
Examples 3-5
An extraction experiment was conducted in the same manner as in Example 2 except that the type of the extractant was changed as shown in Table 1. The extraction conditions and results are summarized in Table 1.
[0047]
[Table 1]

[0048]
【The invention's effect】
As is clear from the above Examples and Comparative Examples, according to the method for producing acetylenic diol of the present invention, by combining a specific reaction solvent and an extractant of the reaction mixture, a by-product ketone condensate can be efficiently produced. A highly pure acetylenic diol compound can be obtained.
[0049]
Moreover, the method for producing acetylene diol of the present invention is excellent in that the loss of the reaction solvent and the extractant is small.

Claims (6)

In a method for producing an acetylenic diol compound by reacting a ketone with acetylene in the presence of an alkali catalyst, an aliphatic hydrocarbon is used as a reaction solvent, and the reaction mixture containing the produced acetylenic diol compound is converted into an aprotic polar solvent. Alternatively, a method for producing an acetylenic diol compound, wherein the acetylene diol compound is obtained by extraction with an extractant comprising methanol. The method for producing an acetylenic diol compound according to claim 1, wherein the ketone is an aliphatic ketone or an aromatic ketone. The method for producing an acetylenic diol compound according to claim 2, wherein the ketone is acetone, methyl ethyl ketone or methyl isobutyl ketone. The method for producing an acetylenic diol compound according to claim 1, wherein the ketone is a cyclic ketone. The method for producing an acetylenic diol compound according to any one of claims 1 to 4, wherein the reaction solvent is a linear or cyclic aliphatic hydrocarbon or a mixture of the same or different species thereof. The aprotic polar solvent is dimethyl sulfoxide, tetramethylene sulfoxide, acetonitrile, N, N-dimethylformamide, N-methyl-2-pyrrolidone or 1,3-dimethyl-2-imidazolidinone. The manufacturing method of acetylene diol compound as described in any one of.