JP3271371B2 - Method for producing diacetin concentrate - Google Patents
Method for producing diacetin concentrateInfo
- Publication number
- JP3271371B2 JP3271371B2 JP14553893A JP14553893A JP3271371B2 JP 3271371 B2 JP3271371 B2 JP 3271371B2 JP 14553893 A JP14553893 A JP 14553893A JP 14553893 A JP14553893 A JP 14553893A JP 3271371 B2 JP3271371 B2 JP 3271371B2
- Authority
- JP
- Japan
- Prior art keywords
- diacetin
- acetin
- triacetin
- mixture
- extraction
- 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.)
- Expired - Fee Related
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、溶剤、可塑剤、合成樹
脂除去剤、湿潤剤等の成分として有用なジアセチン濃縮
物の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a diacetin concentrate useful as a component such as a solvent, a plasticizer, a synthetic resin remover, and a wetting agent.
【０００２】[0002]
【従来の技術】少なくともジアセチンとトリアセチンを
含有するアセチン混合物は、グリセリンのアセチル化に
より製造される。当該アセチル化は、グリセリンと酢酸
又は無水酢酸とを無触媒下又は硫酸、リン酸、パラ−ト
ルエンスルホン酸、酸性イオン交換樹脂等の触媒の存在
下に反応させることで行われる。BACKGROUND OF THE INVENTION Acetin mixtures containing at least diacetin and triacetin are prepared by acetylation of glycerin. The acetylation is performed by reacting glycerin with acetic acid or acetic anhydride in the absence of a catalyst or in the presence of a catalyst such as sulfuric acid, phosphoric acid, para-toluenesulfonic acid, or an acidic ion exchange resin.
【０００３】具体例として、グリセリンに対して特定量
の酢酸をアセチル化剤として使用し、無触媒下、生成す
る水を過剰に存在する酢酸と共に系外に留去する方法が
知られている（特開昭６３−２７４５６号）。[0003] As a specific example, a method is known in which a specific amount of acetic acid is used as an acetylating agent with respect to glycerin, and the produced water is distilled out of the system together with excess acetic acid without a catalyst ( JP-A-63-27456).
【０００４】ジアセチンは、１個の水酸基と２個のアセ
チル基とを持ち、構造上、良好な保湿効果を具備する
等、モノアセチンやトリアセチン等の他のアセチン誘導
体と異なる特性が期待される化合物である。しかしなが
ら、当該反応は逐次反応であるため、一般にアセチル化
を適用してジアセチンのみを得ることは困難である。事
実、上記の公知方法で得られたアセチン混合物中のジア
セチンの濃度は約５３％と低く、ジアセチン特有の効果
を発揮することが困難である。又、高エネルギー消費型
である蒸留工程が必要であるため、工業的製法として
は、尚、改善の余地が認められる。Diacetin is a compound which has one hydroxyl group and two acetyl groups and is expected to have properties different from other acetin derivatives such as monoacetin and triacetin, such as having a good moisturizing effect in structure. is there. However, since the reaction is a sequential reaction, it is generally difficult to obtain only diacetin by applying acetylation. In fact, the concentration of diacetin in the acetin mixture obtained by the above-mentioned known method is as low as about 53%, and it is difficult to exert the effect peculiar to diacetin. In addition, since a distillation step that requires high energy consumption is required, there is still room for improvement as an industrial production method.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、工業的に有
利な条件下で高濃度のジアセチンを含有するアセチン混
合物を得ることができる新規有用な方法を提供すること
を目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a novel and useful method for obtaining an acetylene mixture containing a high concentration of diacetin under industrially advantageous conditions.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記目的
を達成すべくアセチン誘導体に対する各種溶媒の溶解特
性について鋭意検討した結果、特定の溶媒を用いてアセ
チン混合物を抽出処理することにより所定の効果が得ら
れることを見いだし、かかる知見に基づいて本発明を完
成するに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies on the solubility characteristics of various solvents for acetylene derivatives in order to achieve the above object. The present inventors have found that the above effect can be obtained, and have completed the present invention based on such knowledge.
【０００７】即ち、本発明に係るジアセチン濃縮物の製
造方法は、少なくともジアセチンとトリアセチンとを含
有するアセチン混合物からトリアセチンを抽出するに際
し、抽出溶媒として炭素数４〜１８の直鎖状又は分岐鎖
状の飽和若しくは不飽和の脂肪族系炭化水素及び一般式
（１）で示される脂環式炭化水素よりなる群から選ばれ
る１種若しくは２種以上の溶媒を用いることを特徴とす
る。That is, the method for producing a diacetin concentrate according to the present invention is characterized in that when extracting triacetin from an acetin mixture containing at least diacetin and triacetin, a linear or branched C4-C18 extraction solvent is used as an extraction solvent. Characterized in that one or more solvents selected from the group consisting of saturated or unsaturated aliphatic hydrocarbons and alicyclic hydrocarbons represented by the general formula (1) are used.
【０００８】[0008]
【化２】 ［式中、Ａは炭素数４〜１０の飽和又は不飽和の脂肪族
環を示す。Ｒは直鎖状若しくは分岐鎖状の炭素数１〜４
のアルキル基又は直鎖状若しくは分岐鎖状の炭素数２〜
４のアルケニル基を表す。ｍは０〜３の整数を表す。ｍ
が２又は３のとき、夫々Ｒで表される置換基は同一でも
異なっていてもよい。］Embedded image [In the formula, A represents a saturated or unsaturated aliphatic ring having 4 to 10 carbon atoms. R is a linear or branched C1-C4 carbon atom;
An alkyl group or a linear or branched C2-C2
4 represents an alkenyl group. m represents an integer of 0 to 3. m
Is 2 or 3, the substituents represented by R may be the same or different. ]
【０００９】本発明に係るアセチン混合物は、ジアセチ
ン及びトリアセチンとを必須成分とし、その他の成分と
してモノアセチンやグリセリンを含んでいてもよい。The acetin mixture according to the present invention contains diacetin and triacetin as essential components, and may contain monoacetin and glycerin as other components.
【００１０】かかる組成物は、例えば、上記の如くグリ
セリンと酢酸又は無水酢酸とのアセチル化によって得る
ことができる。又、グリセリンと酢酸を反応させ、一
旦、酢酸と生成水を除去後、無水酢酸を加えてもよい。
更に、上記方法で得られたアセチン混合物から蒸留等で
トリアセチンを一部除去したアセチン混合物を用いても
よい。Such a composition can be obtained, for example, by acetylation of glycerin with acetic acid or acetic anhydride as described above. Alternatively, glycerin and acetic acid may be allowed to react with each other, and once acetic acid and produced water may be removed, acetic anhydride may be added.
Further, an acetylene mixture obtained by partially removing triacetin by distillation or the like from the acetylene mixture obtained by the above method may be used.
【００１１】本発明に係る抽出前のアセチン混合物にお
ける各アセチン成分の混在比率は、所定の濃縮効果が得
られる限り特に限定されないものの、通常、ジアセチン
の濃度が３０〜７０重量％である組成物がその抽出操作
上、推奨される。The mixing ratio of each acetin component in the acetylene mixture before extraction according to the present invention is not particularly limited as long as a predetermined concentration effect can be obtained, but usually, a composition having a diacetin concentration of 30 to 70% by weight is used. It is recommended for its extraction operation.
【００１２】飽和脂肪族炭化水素としては、ブタン、ペ
ンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカ
ン、ドデカン、テトラデカン、ヘキサデカン、オクタデ
カン、イソオクタン等が例示され、これらの中でもペン
タン、ヘキサン、ヘプタン、オクタン、イソオクタン等
が好ましい。Examples of the saturated aliphatic hydrocarbon include butane, pentane, hexane, heptane, octane, nonane, decane, dodecane, tetradecane, hexadecane, octadecane, isooctane and the like. Among these, pentane, hexane, heptane, octane, Isooctane and the like are preferred.
【００１３】不飽和脂肪族炭化水素としては、ペンテ
ン、ヘキセン、ヘプテン、オクテン、ノネン、デセン、
ドデセン、テトラデセン、ヘキサデセン、オクタデセン
等が例示され、これらの中でもヘキセン、ヘプテン、オ
クテン、デセン、ドデセン等が好ましい。The unsaturated aliphatic hydrocarbons include pentene, hexene, heptene, octene, nonene, decene,
Examples include dodecene, tetradecene, hexadecene, octadecene and the like, among which hexene, heptene, octene, decene, dodecene and the like are preferable.
【００１４】飽和脂環式炭化水素としては、シクロブタ
ン、シクロペンタン、シクロヘキサン、シクロオクタ
ン、シクロデカン、メチルシクロヘキサン、エチルシク
ロヘキサン等が例示され、これらの中でもシクロペンタ
ン、シクロヘキサン、メチルシクロヘキサン等が好まし
い。Examples of the saturated alicyclic hydrocarbon include cyclobutane, cyclopentane, cyclohexane, cyclooctane, cyclodecane, methylcyclohexane, and ethylcyclohexane. Of these, cyclopentane, cyclohexane, methylcyclohexane and the like are preferable.
【００１５】又、不飽和脂環式炭化水素としては、シク
ロブテン、シクロペンテン、シクロヘキセン、シクロオ
クテン、シクロデセン、メチルシクロヘキセン、エチル
シクロヘキセン等が例示され、これらの中でもシクロヘ
キセン、シクロオクテン、シクロデセン、メチルシクロ
ヘキセン等が好ましい。Examples of the unsaturated alicyclic hydrocarbon include cyclobutene, cyclopentene, cyclohexene, cyclooctene, cyclodecene, methylcyclohexene, ethylcyclohexene and the like. Among these, cyclohexene, cyclooctene, cyclodecene, methylcyclohexene and the like are exemplified. preferable.
【００１６】上記各炭化水素において、所定の炭素数未
満の化合物では、一般に低沸点のため操作上取り扱いが
困難であり、一方、所定の炭素数を越える化合物の場合
には、一般に高沸点のため抽出操作後の除去が困難とな
って、何れも好ましくない。In the above-mentioned hydrocarbons, compounds having less than a predetermined number of carbon atoms are generally difficult to handle because of their low boiling points, and compounds having more than a predetermined number of carbon atoms are generally high in boiling point. Removal after the extraction operation becomes difficult, and neither is preferable.
【００１７】抽出方法としては、回分、連続の何れの方
法でもよく、抽出に用いた溶媒は蒸留等により回収し、
再使用することができる。The extraction method may be either batch or continuous. The solvent used for the extraction is recovered by distillation or the like.
Can be reused.
【００１８】溶媒の使用量は、回分方式の場合、アセチ
ン混合物に対し５〜２００重量倍、好ましくは２０〜１
００重量倍程度であるが、当該使用量は抽出前のアセチ
ン混合物の組成と目的とするジアセチン濃度により適宜
選択することができる。The amount of the solvent used is 5 to 200 times by weight, preferably 20 to 1 times by weight of the acetin mixture in the case of a batch system.
The amount is about 00 times by weight, but the amount can be appropriately selected depending on the composition of the acetin mixture before extraction and the desired diacetin concentration.
【００１９】抽出回数としては、１回で所要溶媒量を用
いた方法でもよく、数回〜数１０回に分けて行ってもよ
い。抽出操作を繰り返すことによりジアセチン濃度を向
上せしめることが可能ではあるが、作業効率面から判断
して、通常、１〜２０回程度の抽出回数が推奨される。The number of extractions may be a method using a required amount of solvent at one time, or may be divided into several to several tens of times. Although it is possible to improve the diacetin concentration by repeating the extraction operation, the number of extractions is generally recommended to be about 1 to 20 times from the viewpoint of work efficiency.
【００２０】抽出温度としては、常温から適用した抽出
溶媒の沸点までの範囲が例示され、具体的には、３０〜
２００℃程度が推奨される。The extraction temperature ranges from room temperature to the boiling point of the applied extraction solvent.
About 200 ° C. is recommended.
【００２１】かくして得られるジアセチン濃縮物は、溶
剤、可塑剤、合成樹脂除去剤、湿潤剤等の成分として適
用される。The diacetin concentrate thus obtained is used as a component such as a solvent, a plasticizer, a synthetic resin remover, and a wetting agent.
【００２２】[0022]
【実施例】以下に、実施例及び比較例を挙げて本発明を
具体的に説明する。尚、各アセチン混合物中のアセチン
混合物の組成（重量％）は、ガスクロマトグラフィーに
よって測定した。The present invention will be specifically described below with reference to examples and comparative examples. The composition (% by weight) of the acetylene mixture in each acetin mixture was measured by gas chromatography.
【００２３】実施例１ トリアセチン／ジアセチン／モノアセチン＝４８／４８
／４の組成のアセチン混合物２５ｇにｎ−ヘキサン１０
０mlを加え、室温下振盪後、分層した。上層を除去し、
下層にｎ−ヘキサンを１００ml加え、同様に抽出操作を
行った。この操作を１２回繰り返した後、下層よりｎ−
ヘキサンを留去したところ、１３ｇのアセチン混合物が
得られた。分析の結果、この混合物の組成は、トリアセ
チン／ジアセチン／モノアセチン＝２６／７０／４であ
った。Example 1 Triacetin / diacetin / monoacetin = 48/48
25 g of an acetin mixture having a composition of
0 ml was added, the mixture was shaken at room temperature, and the layers were separated. Remove the upper layer,
100 ml of n-hexane was added to the lower layer, and extraction was performed in the same manner. After repeating this operation 12 times, n-
Hexane was distilled off to obtain 13 g of an acetin mixture. As a result of analysis, the composition of this mixture was triacetin / diacetin / monoacetin = 26/70/4.
【００２４】実施例２ 抽出溶媒としてシクロヘキサンを用いた他は実施例１と
同様にして処理したところ、トリアセチン／ジアセチン
／モノアセチン＝２７／６９／４の組成のアセチン混合
物１３ｇが得られた。Example 2 The same treatment as in Example 1 was carried out except that cyclohexane was used as the extraction solvent, to obtain 13 g of an acetin mixture having a composition of triacetin / diacetin / monoacetin = 27/69/4.
【００２５】実施例３ 抽出温度を４０℃とした他は実施例１と同様にして処理
したところ、トリアセチン／ジアセチン／モノアセチン
＝１５／８０／５の組成のアセチン混合物１２ｇが得ら
れた。Example 3 The same treatment as in Example 1 was carried out except that the extraction temperature was changed to 40 ° C., to obtain 12 g of an acetin mixture having a composition of triacetin / diacetin / monoacetin = 15/80/5.
【００２６】実施例４ トリアセチン／ジアセチン／モノアセチン＝６１／３８
／１の組成のアセチン混合物を２５ｇ用い、抽出溶媒に
オクタンを１００ml用いて実施例１と同様の操作を２０
回行ったところ、トリアセチン／ジアセチン／モノアセ
チン＝３０／６８／２の組成のアセチン混合物８ｇが得
られた。Example 4 Triacetin / diacetin / monoacetin = 61/38
The same operation as in Example 1 was carried out by using 25 g of an acetin mixture having a composition of 1/1 and using 100 ml of octane as an extraction solvent.
The operation was repeated twice to obtain 8 g of an acetin mixture having a composition of triacetin / diacetin / monoacetin = 30/68/2.
【００２７】実施例５ トリアセチン／ジアセチン／モノアセチン＝２５／７０
／５の組成のアセチン混合物を２５ｇ用い、抽出溶媒に
メチルシクロヘキセンを１００ml用いて実施例１と同様
の操作を８回行ったところ、トリアセチン／ジアセチン
／モノアセチン＝１０／８４／６の組成のアセチン混合
物１７ｇが得られた。Example 5 Triacetin / diacetin / monoacetin = 25/70
The same operation as in Example 1 was performed eight times using 25 g of an acetin mixture having a composition of / 5 and using 100 ml of methylcyclohexene as an extraction solvent, and an acetin mixture having a composition of triacetin / diacetin / monoacetin = 10/84/6 was obtained. 17 g were obtained.
【００２８】実施例６ トリアセチン／ジアセチン／モノアセチン＝４６／５１
／３の組成のアセチン混合物を２５ｇ用い、抽出溶媒に
１−ドデセンを１２５ml用いて実施例１と同様の操作を
１５回行ったところ、トリアセチン／ジアセチン／モノ
アセチン＝１１／８４／５の組成のアセチン混合物１１
ｇが得られた。Example 6 Triacetin / diacetin / monoacetin = 46/51
When the same operation as in Example 1 was performed 15 times using 25 g of an acetin mixture having a composition of / 3 and using 125 ml of 1-dodecene as an extraction solvent, an acetin having a composition of triacetin / diacetin / monoacetin = 11/84/5. Mixture 11
g was obtained.
【００２９】比較例１ 実施例１の組成のアセチン混合物２５ｇに対し、ベンゼ
ン１００mlを抽出溶媒として用いたところ、振盪後、系
は均一となり、ジアセチンは濃縮されなかった。Comparative Example 1 When 25 ml of the acetin mixture having the composition of Example 1 was used with 100 ml of benzene as an extraction solvent, the system became homogeneous after shaking, and diacetin was not concentrated.
【００３０】比較例２ ベンゼンの代わりにクロロホルムを用い、比較例１に準
じて抽出を行ったところ、振盪後、系は均一となり、ジ
アセチンは濃縮されなかった。Comparative Example 2 Extraction was performed according to Comparative Example 1 using chloroform instead of benzene. After shaking, the system became homogeneous and diacetin was not concentrated.
【００３１】[0031]
【発明の効果】本発明に係る抽出操作を施すことによ
り、工業的に有利な条件下でアセチン混合物中のジアセ
チンを濃縮することができる。By performing the extraction operation according to the present invention, diacetin in the acetylene mixture can be concentrated under industrially advantageous conditions.
Claims (1)
を含有するアセチン混合物からトリアセチンを抽出する
に際し、抽出溶媒として炭素数４〜１８の直鎖状又は分
岐鎖状の飽和若しくは不飽和の脂肪族系炭化水素及び一
般式（１）で示される脂環式炭化水素よりなる群から選
ばれる１種若しくは２種以上の溶媒を用いることを特徴
とするジアセチン濃縮物の製造方法。 【化１】 ［式中、Ａは炭素数４〜１０の飽和又は不飽和の脂肪族
環を示す。Ｒは直鎖状若しくは分岐鎖状の炭素数１〜４
のアルキル基又は直鎖状若しくは分岐鎖状の炭素数２〜
４のアルケニル基を表す。ｍは０〜３の整数を表す。ｍ
が２又は３のとき、夫々Ｒで表される置換基は同一でも
異なっていてもよい。］When extracting triacetin from an acetin mixture containing at least diacetin and triacetin, a linear or branched saturated or unsaturated aliphatic hydrocarbon having 4 to 18 carbon atoms is used as an extraction solvent. A method for producing a diacetin concentrate, comprising using one or more solvents selected from the group consisting of alicyclic hydrocarbons represented by the general formula (1). Embedded image [In the formula, A represents a saturated or unsaturated aliphatic ring having 4 to 10 carbon atoms. R is a linear or branched C1-C4 carbon atom;
An alkyl group or a linear or branched C2-C2
4 represents an alkenyl group. m represents an integer of 0 to 3. m
Is 2 or 3, the substituents represented by R may be the same or different. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14553893A JP3271371B2 (en) | 1993-05-24 | 1993-05-24 | Method for producing diacetin concentrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14553893A JP3271371B2 (en) | 1993-05-24 | 1993-05-24 | Method for producing diacetin concentrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06329587A JPH06329587A (en) | 1994-11-29 |
| JP3271371B2 true JP3271371B2 (en) | 2002-04-02 |
Family
ID=15387514
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14553893A Expired - Fee Related JP3271371B2 (en) | 1993-05-24 | 1993-05-24 | Method for producing diacetin concentrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3271371B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PT2931696T (en) * | 2012-12-11 | 2018-11-29 | Bracco Imaging Spa | Continuous process for the preparation of (s)-2-acetyloxypropionic acid |
-
1993
- 1993-05-24 JP JP14553893A patent/JP3271371B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06329587A (en) | 1994-11-29 |
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