JPS62198651A - Hydrogen-bonding molecular clathrate complex and separation of solvent - Google Patents
Hydrogen-bonding molecular clathrate complex and separation of solventInfo
- Publication number
- JPS62198651A JPS62198651A JP4242686A JP4242686A JPS62198651A JP S62198651 A JPS62198651 A JP S62198651A JP 4242686 A JP4242686 A JP 4242686A JP 4242686 A JP4242686 A JP 4242686A JP S62198651 A JPS62198651 A JP S62198651A
- Authority
- JP
- Japan
- Prior art keywords
- dimethylformamide
- monool
- diol
- clathrate
- group
- 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.)
- Pending
Links
- 238000000926 separation method Methods 0.000 title claims abstract description 14
- 239000002904 solvent Substances 0.000 title claims abstract description 12
- 238000010668 complexation reaction Methods 0.000 title 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 231
- 238000010521 absorption reaction Methods 0.000 claims abstract description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- 150000002009 diols Chemical class 0.000 claims abstract description 17
- 238000000862 absorption spectrum Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 21
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000012046 mixed solvent Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 12
- 238000003795 desorption Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 210000003000 inclusion body Anatomy 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MFEWNFVBWPABCX-UHFFFAOYSA-N 1,1,2,2-tetraphenylethane-1,2-diol Chemical compound C=1C=CC=CC=1C(C(O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(O)C1=CC=CC=C1 MFEWNFVBWPABCX-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MZHJJOMWLPIVFA-UHFFFAOYSA-N [Na].C#C Chemical group [Na].C#C MZHJJOMWLPIVFA-UHFFFAOYSA-N 0.000 description 2
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- PLFFHJWXOGYWPR-HEDMGYOXSA-N (4r)-4-[(3r,3as,5ar,5br,7as,11as,11br,13ar,13bs)-5a,5b,8,8,11a,13b-hexamethyl-1,2,3,3a,4,5,6,7,7a,9,10,11,11b,12,13,13a-hexadecahydrocyclopenta[a]chrysen-3-yl]pentan-1-ol Chemical compound C([C@]1(C)[C@H]2CC[C@H]34)CCC(C)(C)[C@@H]1CC[C@@]2(C)[C@]4(C)CC[C@@H]1[C@]3(C)CC[C@@H]1[C@@H](CCCO)C PLFFHJWXOGYWPR-HEDMGYOXSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- ZWPWLKXZYNXATK-UHFFFAOYSA-N bis(4-methylphenyl)methanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=C(C)C=C1 ZWPWLKXZYNXATK-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- -1 dimethylformamide diacetylene diol Chemical compound 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011907 photodimerization Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Landscapes
- Extraction Or Liquid Replacement (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はゾメチμホルムアミドと水素結合を介して結合
するジオールあるいはモノオールとからなる分子包接錯
体及びこれを用いた溶剤の分離方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a molecular inclusion complex consisting of zomethyμ formamide and a diol or monool bonded via hydrogen bonds, and a method for separating solvents using the same.
（従来技術）
ある分子が他の分子を取シ込んで錯体を形成するとき、
この錯体を分子包接錯体といい、前者の分子をホスト分
子、後者の分子をゲスト分子という。(Prior art) When a molecule incorporates another molecule to form a complex,
This complex is called a molecular inclusion complex, and the former molecule is called a host molecule, and the latter molecule is called a guest molecule.
１、１．６．６−テトフフエニμヘキサ−λ４−ジイン
−１，６−シオー〃（以下「ジアセチレンジオ−μ」と
いう）などのジオール類が、種々の溶剤や低分子有機化
合物と分子包接錯体を形成すること及びこれらを立体異
性体の分割例えばラセミ体からの光学活性体の分割に利
用できることが知られている。Diols such as 1,1.6.6-tetofpheniμhexa-λ4-diyne-1,6-thio (hereinafter referred to as “diacetylenedio-μ”) can be mixed with various solvents and low-molecular organic compounds in molecular packaging. It is known that tangential complexes can be formed and that these can be used for the resolution of stereoisomers, such as the resolution of optically active forms from racemates.
また、ジメチルホルムアミドとジオール類との分子包接
錯体に関してはジメチルホルムアミトドジアセチレンジ
オールとの分子包接錯体が知られている（日本化学会誌
Ａ２．２３９．１９８３）。Regarding the molecular inclusion complex of dimethylformamide and diols, a molecular inclusion complex with dimethylformamide diacetylene diol is known (Journal of the Chemical Society of Japan A2.239.1983).
またジメチルホルムアミドと他の液体との混合液からジ
メチルホルムアミドを分離する方法としては通常蒸留法
が採用されている。Further, a distillation method is generally employed as a method for separating dimethylformamide from a mixed solution of dimethylformamide and other liquids.
しかしながら、ジメチルホルムアミドとジアセチレンジ
オ−μとからなる分子包接錯体を加熱して該分子包接錯
体からジメチルホルムアミドを脱離させる場合、脱離速
度が非常に遅い。However, when dimethylformamide is removed from the molecular inclusion complex consisting of dimethylformamide and diacetylene di-μ by heating, the rate of removal is very slow.
従って、ジアセチレンジオ−μをホスト分子としジメチ
ルホルムアミドをゲスト分子とする分子包接錯体を利用
して、分子包接錯体の形成とジメチルホルムアミドの脱
離の繰シ返しによってジメチルホルムアミドを分離・回
収することは極めて難しい。Therefore, by using a molecular inclusion complex with diacetylene diio-μ as a host molecule and dimethylformamide as a guest molecule, dimethylformamide is separated and recovered by repeating the formation of the molecular inclusion complex and the elimination of dimethylformamide. It is extremely difficult to do so.
また蒸留法によって混合液からジメチルホルムアミドを
分離する方法は二ネμギーコストがかかシ過ぎるという
問題がある。Furthermore, the method of separating dimethylformamide from a mixed solution by distillation has the problem of being too expensive.
本発明の目的は、ジメチルホルムアミドと分子包接錯体
を形成するホスト分子について検討し、分子包接錯体の
形成とゲスト分子（ジメチルホルムアミド）の脱離が容
易な分子包接錯体を提供することにちゃ、また該分子包
接錯体を利用して混合液中からジメチルホルムアミドを
低コストで分離・回収可能な溶剤分離方法を提供するこ
とにある。The purpose of the present invention is to study host molecules that form a molecular inclusion complex with dimethylformamide, and to provide a molecular inclusion complex that facilitates the formation of a molecular inclusion complex and the detachment of a guest molecule (dimethylformamide). Another object of the present invention is to provide a solvent separation method capable of separating and recovering dimethylformamide from a liquid mixture at low cost using the molecular inclusion complex.
本発明はジメチルホルムアミドとジオ−／Ｉ／−４たは
モノオールとからなる分子包接錯体であって、該分子包
接錯体におけるジオ−／Ｌ／またはモノオールのＯＨ基
の伸縮振動に帰属される赤外吸収スペクトルの少なくと
もひとつの吸収ピーク位置（以下「包接体のＯＨ基吸収
ピーク位釦という）が、ジオ−μまたはモノオールのＯ
Ｈ基の伸縮振動に帰属される赤外吸収スペクトルの吸収
ピーク位置（以下「ホストのＯＨ基膜吸収ピーク位置と
いう）に対して１００〜２３０ｔＭｔ−１低波数側に移
動してなることを特徴とする分子包接錯体に関し、さら
に、ホストのＯＨ基吸収ピークの位置に対して１００〜
２３０ ｃｍ−”低波数側に移動した位置にＯＨ基の吸
収ピークを少なくともひとつ有するジメチルホルムアミ
ドとジオールまたはモノオールとからなる分子包接錯体
を利用する溶剤分離方法であって、該分子包接錯体を形
成しうるジオ−／Ｉ／またはモノオールを、ジメチルホ
ルムアミド含有液と接触させて分子包接錯体を形成し、
続いて該分子包接錯体を膣液から分離・回収し、更に該
分子包接錯体（以下「包接体」という）からジメチルホ
ルムアミドを脱離させることを特徴とする溶剤分離方法
に関する。The present invention relates to a molecular inclusion complex consisting of dimethylformamide and di-/I/-4 or monool, which is attributed to the stretching vibration of the OH group of di-/L/ or monol in the molecular inclusion complex. At least one absorption peak position of the infrared absorption spectrum (hereinafter referred to as the OH group absorption peak position button of the inclusion complex) is located at the O of the di-μ or monool.
It is characterized by being shifted to the lower wavenumber side by 100 to 230 tMt-1 with respect to the absorption peak position of the infrared absorption spectrum attributed to the stretching vibration of the H group (hereinafter referred to as the "host OH base film absorption peak position"). Regarding the molecular inclusion complex, further, 100 ~
230 cm-" A solvent separation method using a molecular inclusion complex consisting of dimethylformamide and a diol or monool having at least one absorption peak of an OH group at a position shifted to the lower wave number side, the molecular inclusion complex comprising: contacting a di-/I/or monool that can form a dimethylformamide with a dimethylformamide-containing solution to form a molecular inclusion complex;
The present invention relates to a solvent separation method characterized in that the molecular inclusion complex is subsequently separated and recovered from vaginal fluid, and further dimethylformamide is eliminated from the molecular inclusion complex (hereinafter referred to as "inclusion complex").
本発明において用いられるジオ−／Ｉ／ｌたはモノオー
ルとしては、水素結合によってジメチルホルムアミドと
包接体を形成しうる物質であって、該包接体のＯＨ基膜
吸収ピーク位置ホストの０Ｈ１ｉ吸収ピ一ク位置に対す
る低波数側への移動量（以下「ΔνＯＨＪ という）
が１００〜２３０１Ｍ−’である物質を挙げることがで
きる。The di-/I/l or monool used in the present invention is a substance that can form a clathrate with dimethylformamide through hydrogen bonding, and the OH base film absorption peak position of the clathrate is 0H1i of the host. Amount of movement toward the lower wavenumber side relative to the absorption peak position (hereinafter referred to as "ΔνOHJ")
is 100 to 2301 M-'.
このジオールまたはモノオー／Ｌ／（以下「ホスト」と
いう）は通常、常温で固体であシ、およそ５１００〜３
６００ ｅｒａ−”の位置にＯＨ基の伸縮振動に帰属さ
れる赤外吸収スペクトμの吸収ピークを有している。This diol or monool/L/ (hereinafter referred to as "host") is usually solid at room temperature and has a molecular weight of approximately 5100 to 3
It has an absorption peak in the infrared absorption spectrum μ attributable to the stretching vibration of the OH group at the position of 600 era-''.
その例として一般式（１）または（２）で表わされる化
合物を挙げることができる。Examples include compounds represented by general formula (1) or (2).
一般式（１）、（２）においてＲは水素原子またはメチ
ル基である。（１）式においてＲが全て水素原子の化合
物及びＲが全てメチル基の化合物はそれツレベンゾフェ
ノン及び４．４′−ジメチルベンゾフェノンの光二量化
反応によって合成することができる結晶性化合物である
。In general formulas (1) and (2), R is a hydrogen atom or a methyl group. In formula (1), the compound in which all R's are hydrogen atoms and the compound in which all R's are methyl groups are crystalline compounds that can be synthesized by photodimerization reaction of trebenzophenone and 4,4'-dimethylbenzophenone.
また（２）式においてＲが水素原子のものは、λ２’、
４．４’−テトラメチルベンゾフェノンとアセチレンナ
トリウムとの反応によってまたＲがメチル基のものはλ
′２：４．４′−テトラメチルベンゾフェノンとメチμ
アセチレンナトリウムとの反応によって合成できる結晶
性化合物である。In addition, in formula (2), when R is a hydrogen atom, λ2',
4. By the reaction of 4'-tetramethylbenzophenone with sodium acetylene, when R is a methyl group, λ
'2:4.4'-tetramethylbenzophenone and methyμ
It is a crystalline compound that can be synthesized by reaction with sodium acetylene.
本発明の包接体はホストのＯＨ基とゲストであるジメチ
ルホルムアミドが水素結合によって一定割合で結合した
物質であシ、ホスト分子とジメチμホｐムアミ、ド分子
との分子間の結合割合ハ、ホストがモノオールの場合は
１：１、−ｉたホストがジオ−〃の場合は１：２または
１：１である。The clathrate of the present invention is a substance in which the host OH group and the guest dimethylformamide are bonded at a certain ratio through hydrogen bonds, and the intermolecular bonding ratio between the host molecule and the dimethyl μformamide or do molecule is , 1:1 when the host is monool, and 1:2 or 1:1 when the -i host is geo-.
ホストのＯＨ基の部分にジメチルホルムアミドが結合す
るとホストのＯＨ基吸収ピーク位置は低波数側へ移動す
るが、本発明の包接体においてＯＨ基吸収ピークの移動
量ΔνＯＨは１００〜２５０ ｃｍ−”の範囲である。When dimethylformamide binds to the OH group portion of the host, the OH group absorption peak position of the host shifts to the lower wavenumber side, but in the clathrate of the present invention, the shift amount ΔνOH of the OH group absorption peak is 100 to 250 cm. is within the range of
△νＯＨが１００ ｔｙｎ−’未満の場合はホストとジ
メチ／Ｌ／示ｐムアミドとの結合力が弱いので包接体を
安定に形成することができず好ましくない。またΔνＯ
Ｈが２３０５１−”より大きい場合はホストとジメチル
ホルムアミドとの結合力が強く包接体の安定性が良すぎ
るので、ホストからジメチルホルムアミドを脱離させる
ことが難しく脱離速度が遅くなるので好ましくない。When ΔνOH is less than 100 tyn-', the bonding force between the host and the dimethy/L/dimamide is weak, making it impossible to stably form the clathrate, which is not preferable. Also ΔνO
If H is larger than 23051-'', the binding force between the host and dimethylformamide is strong and the stability of the clathrate is too good, making it difficult to eliminate dimethylformamide from the host and slowing down the rate of elimination, which is not preferable. .
本発明の包接体はジメチルホルムアミドと小ストを接触
させ、水素結合させることによって得ることができる。The clathrate of the present invention can be obtained by bringing dimethylformamide into contact with small molecules to form a hydrogen bond.
その際ジメチルホルムアミドは単独液でもよく、他の液
体との混合液であってもよい。この包接体の形成は室温
でも進行するが、必要に応じて加熱し高温下にて実施し
、包接体の形成を促進することもできる。In this case, dimethylformamide may be used alone or as a mixture with other liquids. The formation of this inclusion body proceeds even at room temperature, but if necessary, the formation of the inclusion body can be promoted by heating at a high temperature.
包接体の形成温度としては、常温〜１００℃程度の条件
を、また時間としては１〜２０時間程度の条件を採用す
ることができる。As the temperature for forming the clathrate, a condition of room temperature to about 100°C can be adopted, and as the time, a condition of about 1 to 20 hours can be adopted.
尚、ホストの種類やジメチルホルムアミド含有液の種類
によってホストの溶解度は変化するが、ホストが未溶解
状態であっても該包接体の形成はほぼ充分に進行する。Although the solubility of the host changes depending on the type of host and the type of dimethylformamide-containing liquid, the formation of the clathrate proceeds almost satisfactorily even when the host is in an undissolved state.
包接体が形成された後は必要に応じて冷却して包接体を
固相状態とし、液中から包接体を固液分離することによ
って包接体を得ることができる。固液分離後、必要に応
じて水洗、乾燥等の操作を適用してもよい。After the clathrate is formed, the clathrate can be obtained by cooling the clathrate as necessary to bring it into a solid state, and separating the clathrate from the liquid into solid and liquid. After solid-liquid separation, operations such as washing with water and drying may be applied as necessary.
次に本発明の包接体を利用する溶剤分離方法について述
べる。Next, a solvent separation method using the clathrate of the present invention will be described.
本発明の包接体の形成を利用してジメチルホルムアミド
と他の液体とからなる混合液からジメチルホルムアミド
を選択的に回収することができる。Dimethylformamide can be selectively recovered from a mixture of dimethylformamide and other liquids by utilizing the formation of inclusion bodies of the present invention.
前記混合液中の他の液体としては、本願発明のホストと
包接体を形成しない液体、ちるいは本願発明のホストと
包接体を形成しうるが、ジメチルホルムアミドと比較す
ると包接体形成能が劣る液体を挙げることができる。そ
の具体例としてたとえば水、酢酸等を挙げることができ
、ジメチルホルムアミドを５０〜１チ程度含有するこれ
らの混合液等からジメチμホルムアミドを選択的に回収
することができる。The other liquid in the mixed liquid may be a liquid that does not form a clathrate with the host of the present invention, or a liquid that may form a clathrate with the host of the present invention, but compared with dimethylformamide, it is less likely to form a clathrate. Liquids with inferior performance can be mentioned. Specific examples include water, acetic acid, etc., and dimethyl μformamide can be selectively recovered from a mixed solution of these containing about 50 to 1% dimethylformamide.
本発明のジメチルホルムアミド含有混合液（以下「ＤＭ
Ｆ液」という）からジメチルホルムアミドを分離・回収
する方法においては、まずホストをＤＭＦ液と接触させ
ることによす包接体を形成する。Dimethylformamide-containing mixture of the present invention (hereinafter referred to as "DM")
In a method for separating and recovering dimethylformamide from a DMF solution (referred to as "F solution"), a host is first brought into contact with a DMF solution to form a clathrate.
接触方法としては、パッチ法あるいは充填塔法を採用す
ることができる。As the contact method, a patch method or a packed column method can be adopted.
パッチ法の場合はＤＭＦ液に所定量のホストを添加し、
必要に応じて加熱、攪拌等を行なうことができる。ホス
トの添加量は任意であるが、ジメチμホ〜ムアミド１分
子に対してホスト分子中の包接体形成に関与するＯＨ基
が１ヶ以上になるような割合でホストを過剰に添加する
ことが好ましい。またこの時の温度はおよそ常温〜１０
０℃程度、時間はおよそ１〜２０時間程度であることが
好ましい。In the case of the patch method, a predetermined amount of host is added to the DMF solution,
Heating, stirring, etc. can be performed as necessary. The amount of host added is arbitrary, but the host should be added in excess at a ratio such that there is one or more OH group involved in inclusion body formation in the host molecule per molecule of dimethymuamide. is preferred. Also, the temperature at this time is approximately room temperature ~ 10
Preferably, the temperature is about 0°C and the time is about 1 to 20 hours.
充填塔法を採用する場合は、ＤＭＦ液の温度を適宜調節
する等して、ＤＭＦ液に対するホストの溶解度が小さい
条件を採用し、ＤＭＦ液を通液することが好ましい。充
填塔内のホストは固定層のみならず流動層とすることも
可能である。尚、充填塔法においては複数個の充填塔を
直列に接続して行なうことが好ましい。When employing the packed column method, it is preferable to adjust the temperature of the DMF liquid as appropriate so that the solubility of the host in the DMF liquid is low, and to pass the DMF liquid through the DMF liquid. The host in the packed column can be not only a fixed bed but also a fluidized bed. In the packed column method, it is preferable to connect a plurality of packed columns in series.
充填塔法においてはホスト分子の充填量、充填塔の数、
ＤＭＦ液の通液速度等を変えることによって、ホスト分
子とＤＭＦ液との接触時間を任意に調節することができ
る。In the packed column method, the amount of packing of host molecules, the number of packed columns,
By changing the flow rate of the DMF liquid, etc., the contact time between the host molecules and the DMF liquid can be adjusted as desired.
このようにして充填塔内においである程度の包接体が形
成された段階で包接体とＤＭＦ液とを分離する。充填塔
内には包接体がホストとの混合物として存在し、両者は
通常共に固相でちるので、包接体はホストとの混合物と
してＤＭＦ液から固液分離される。具体的には充填塔へ
のＤＭＦ液の通液を止め充填塔からＤＭＦ液を抜くこと
によって固液分離を行々うことができる。In this way, when a certain amount of inclusion bodies are formed in the packed column, the inclusion bodies and the DMF liquid are separated. In the packed column, the clathrate exists as a mixture with the host, and since both of them are usually in the solid phase, the clathrate is separated into a solid-liquid from the DMF liquid as a mixture with the host. Specifically, solid-liquid separation can be performed by stopping the flow of the DMF liquid to the packed tower and removing the DMF liquid from the packed tower.
パッチ法の場合において、包接体のＤＭＦ液に対する溶
解度が高いときは固液分離時の温度を極力低下させて溶
解度を減少させ固液分離を行なうことが好ましい。固液
分離方法としては濾過、遠心分離等の公知の方法を適用
することができる。In the case of the patch method, when the solubility of the clathrate in the DMF liquid is high, it is preferable to lower the temperature during solid-liquid separation as much as possible to reduce the solubility and perform solid-liquid separation. As a solid-liquid separation method, known methods such as filtration and centrifugation can be applied.
固液分離等によって回収された包接体は次に脱離工程に
移される。包接体からジメチルホルムアミドを脱離させ
る方法としては通常加熱法が採用される。加熱温度とし
てはホストの融点以下の適当な温度とすることができる
。温度が高いと脱離速度は大きいがエネルギーコストが
余分にかかるのでこれらの点を考慮して脱離温度を選定
すればよい。The clathrates recovered by solid-liquid separation etc. are then transferred to a desorption step. A heating method is usually employed as a method for eliminating dimethylformamide from the inclusion body. The heating temperature can be any suitable temperature below the melting point of the host. If the temperature is high, the desorption rate is high, but the energy cost is extra, so the desorption temperature should be selected taking these points into consideration.
好ましい脱離温度として５０〜８０℃程度の条件を挙げ
ることができる。この程度の温度はたとえば工場等にお
いて実際にＤＭＦ液を使用している工程や、他の工程で
発生する熱であって比較的利用価値が乏しいために廃熱
として廃棄されている熱等を有効利用するととくよって
得ることが可能であシ、蒸留法と比較すると溶剤回収コ
ストを低下させることができる。A preferable desorption temperature is about 50 to 80°C. This level of temperature makes it possible to utilize heat that is generated in processes that actually use DMF liquid in factories, etc., or in other processes, and that is discarded as waste heat because it has relatively little utility value. When used, it can be obtained by combing, and the cost of recovering the solvent can be lowered compared to the distillation method.
また脱離時の糸の圧力は常圧でもよいが、減圧下で実施
すると脱離速度が大きくなるので必要に応じて減圧下で
実施することができる。Further, the pressure of the yarn during detachment may be normal pressure, but since the detachment speed increases when carried out under reduced pressure, it can be carried out under reduced pressure if necessary.
充填塔方式の場合は充填塔を加熱可能な構造とし、また
は更に減圧可能な構造としておけば充填塔内においてジ
メチルホルムアミドを脱ｍすることができる。In the case of a packed column system, dimethylformamide can be removed in the packed column if the packed column has a structure that allows heating or a structure that allows pressure reduction.
このようにしてジメチルホルムアミドを脱離することに
よって回収されたホストは再使用が可能であり、再び包
接体の形成に利用される。The host recovered by removing dimethylformamide in this manner can be reused and used again to form an inclusion complex.
〔実施例］ 以下実施例により本発明を更に具体的に説明する。〔Example] The present invention will be explained in more detail with reference to Examples below.
実施例１
１、１．２． ｆｉ−テトラフェニ／ｌ／−１，２−エ
タンジオ−／Ｉ／（以下「ペンブピナコーμ」という）
１、０ Ｉｌ（２，７５Ｘ １０””モ／Ｌ／）をジメ
千〃ホ〃ムアミドａｎｄ中に入れ１００℃で１０分間加
熱溶解した後室温まで冷却し１２時間放置した。Example 1 1, 1.2. fi-tetrapheny/l/-1,2-ethanedio-/I/ (hereinafter referred to as "penbupinacoo μ")
1,0 Il (2,75X 10"" mo/L/) was placed in dimethicamide and dissolved by heating at 100° C. for 10 minutes, then cooled to room temperature and left for 12 hours.
析出した結晶をＰ集し、水洗後室温で乾燥すると白色固
体１．１２９が得られた。この白色固体をＴＧＡ−ＤＴ
Ａ分析したところ９０’Ｃ付近でジメチルアミドが放出
され該白色固体が包接体であることが確認された。更に
加熱するとベンゾピナコールの融解点と温度の同じ１９
０℃で融解した。The precipitated crystals were collected, washed with water, and dried at room temperature to obtain 1.129 of a white solid. TGA-DT this white solid
As a result of A analysis, dimethylamide was released at around 90'C, and it was confirmed that the white solid was an clathrate. When heated further, the melting point is the same as that of benzopinacol19.
It melted at 0°C.
第１図、第２図にＫＢｒ綻剤法で測定したベンゾピナコ
ールと前記白色固体の赤外吸収スペクトμを示す。第１
図で３５８０ｃ！Ｒ−”に観察される吸収はペンゾピナ
コ−〃のＯＨ基の伸縮振動による吸収であシ、第２図で
はこのピークが減少し、約５４５０ｃｍ’に新なＯＨ基
の伸縮振動による吸収ピークが出現しており、ＯＨ基吸
収ピークの移動量△νＯＨは約１３ｏｃｒｎ−１である
。Figures 1 and 2 show the infrared absorption spectra μ of benzopinacol and the white solid measured by the KBr resolving method. 1st
3580c in the diagram! The absorption observed at R-'' is due to the stretching vibration of the OH group of penzopinaco-〃; in Figure 2, this peak decreases, and a new absorption peak due to the stretching vibration of the OH group appears at approximately 5450 cm'. The amount of shift ΔνOH of the OH group absorption peak is about 13ocrn-1.
また１６６０α−１付近にはジメチルアミドの力μボニ
／Ｌ／基の伸縮振動による吸収ピークがみられる。Further, an absorption peak due to the stretching vibration of the force μboni/L/group of dimethylamide is observed near 1660α-1.
ｄ−クロロホルム溶媒中、室温下”Ｈ−ＮＭＲ測定での
プロトン積分値比から該包接体がペンゾビナコーμｍ分
子とジメチルホルムアミド２分子とからなることが確認
された。It was confirmed from the proton integral value ratio in H-NMR measurement in d-chloroform solvent at room temperature that the clathrate consisted of a penzovinacor μm molecule and two molecules of dimethylformamide.
次にこの包接体１０■を微粉砕し、常圧下７０℃での重
量変化を測定した。重量変化がジメチルホルムアミドの
脱離によるものとして、ジメチルホルムアミド脱離量の
経時変化を求め第３図に示した。脱離開始後５０分間で
ジメチルホルムアミドがほぼ１００チ完全に脱離した。Next, 10 cm of this clathrate was pulverized and the change in weight at 70° C. under normal pressure was measured. Assuming that the weight change was due to the elimination of dimethylformamide, the change over time in the amount of dimethylformamide eliminated was determined and shown in FIG. Approximately 100 units of dimethylformamide were completely desorbed within 50 minutes after the desorption started.
次に脱離工程に督いて残存した白色固体の赤外吸収スペ
クトルを測定したところベンゾピナコールと全く同じ吸
収スベク）／しが得られた。Next, when the infrared absorption spectrum of the white solid that remained after the desorption step was measured, an absorption spectrum exactly the same as that of benzopinacol was obtained.
実施例２〜４
実施例１と同様にして第１表のｙオーＩｖまたはモノオ
ール各々１．０９をジメチルホルムアミド１，５−中で
加熱溶解し、室温下で１２時間放置し包接体を得た。続
いて実施例１と同様にして、加熱によるジメチルホルム
アミドの脱離、”Ｈ−ＮＭＲ測定及び赤外吸収スペクト
ル測定を実施し、包接比とΔνＯＨを求めた。Examples 2 to 4 In the same manner as in Example 1, 1.09 of each of yO Iv or monool shown in Table 1 was dissolved by heating in dimethylformamide 1,5-, and the mixture was left at room temperature for 12 hours to dissolve the clathrate. Obtained. Subsequently, in the same manner as in Example 1, desorption of dimethylformamide by heating, H-NMR measurement, and infrared absorption spectrum measurement were performed to determine the inclusion ratio and ΔνOH.
実施例５については実施例１と同様にしてジメチルホル
ムアミド脱離量の経時変化を求め第３図に示した。Regarding Example 5, the change over time in the amount of dimethylformamide eliminated was determined in the same manner as in Example 1, and is shown in FIG.
比較例１．２
第１表のジオールを用い実施例２と同様にして包接体を
形成し、包接比と△νＯＨを求めた。Comparative Example 1.2 An inclusion body was formed using the diols shown in Table 1 in the same manner as in Example 2, and the inclusion ratio and ΔνOH were determined.
比較例２については実施例１と同様にしてジメチルホル
ムアミド脱離量の経時変化を求め第３図に示した。Regarding Comparative Example 2, the change over time in the amount of dimethylformamide eliminated was determined in the same manner as in Example 1, and is shown in FIG.
第 １ 表
（注１）ホスト分子ニジメチルホルムアミド分子の結合
比実施例５
ペンゾビナコーＮ５．１３９ （０，０１３６ｍｏｌ
）を十分微粉砕し、ジメチルホμムアミドヲ２４重量％
含有する水溶液８．０−中に入れ室温で一麗夜攪拌した
。次いで固形分をｆ取し、室温で乾燥すると、白色固体
５．５０９が得られた。該白色固体の赤外吸収スペクト
ルから包接体が形成されていることが確認できた。Table 1 (Note 1) Binding ratio of host molecule dimethylformamide molecule Example 5 Penzobinacor N5.139 (0,0136 mol
) was thoroughly pulverized, and 24% by weight of dimethylformamide was added.
The mixture was poured into an aqueous solution containing 8.0 g of chloride and stirred overnight at room temperature. Then, the solid content was taken out and dried at room temperature to obtain 5.509 of a white solid. It was confirmed from the infrared absorption spectrum of the white solid that an clathrate was formed.
一方、Ｐ液濃度をガスクロマトグラフィーで定量すると
、ジメチルホルムアミドの濃度は１＆５重ｔチであった
。On the other hand, when the concentration of P solution was determined by gas chromatography, the concentration of dimethylformamide was found to be 1 and 5 times.
この白色固体を温度８０℃、０．５ ｗ Ｈｇの減圧下
で１時間加熱し、蒸発物を液体窒素冷却トラップで捕集
したところ、１１５２．９のジメチルホルムアミドが得
られた。This white solid was heated at a temperature of 80° C. under a reduced pressure of 0.5 w Hg for 1 hour, and the evaporated material was collected in a liquid nitrogen cooling trap, yielding 1152.9 dimethylformamide.
又、蒸発残留物は赤外吸収スペクトルから、ペンゾピナ
コーｐであることが確認され、包接体からジメチルホル
ムアミドがほぼ完全に脱離されていることが確認された
。Further, the evaporation residue was confirmed to be penzopinako p from the infrared absorption spectrum, and it was confirmed that dimethylformamide was almost completely eliminated from the clathrate.
次に前記のｆ液に対してペンゾピナコーμ５．０ｇを添
加し、同様にして包接体の形成、ｒ液回収、脱離の操作
を合計６回縁シ返したところＦＷ中のジメチルホルムア
ミドの濃度は五２重量％となった。Next, 5.0 g of Penzopinakor μ was added to the f-liquid, and the operations of formation of the clathrate, collection of the r-liquid, and desorption were repeated six times in total in the same manner, resulting in the concentration of dimethylformamide in the FW. was 52% by weight.
以上説明したように本発明のジオールあるいはモノオー
ルとジメチルホルムアミドとからなる包接体はジメチル
ホルムアミドを比較的安定に取り込んでいるとともに、
ジメチルホルムアミドの脱離特性が優れている。As explained above, the clathrate consisting of diol or monool and dimethylformamide of the present invention incorporates dimethylformamide relatively stably, and
Excellent desorption properties for dimethylformamide.
またこの包接体を利用してジメチルホルムアミド含有液
からジメチルホルムアミドを分離する場合、包接体形成
工程においては包接体の形成が容易であり、かつ脱離工
程においては比較的低い温度でジメチルホルムアミドを
脱離することができるのでジメチルホルムアミドの分離
・回収を低コストで行なうことができる。Furthermore, when dimethylformamide is separated from a dimethylformamide-containing solution using this clathrate, the clathrate can be easily formed in the clathrate formation step, and dimethyl Since formamide can be eliminated, dimethylformamide can be separated and recovered at low cost.
第１図はペンゾピナコーμの赤外吸収スペクトル、第２
図はペンゾビナコーμとジメチルホルムアミドから得ら
れる包接体の赤外吸収スペクトμを示す。第３図は、ジ
オ−μあるいはモノオールとジメチルホルムアミドとか
らなる包接体を常圧下、７０℃で加熱したときのジメチ
ルホルムアミドの脱離量の経時変化を示す。Figure 1 is the infrared absorption spectrum of Penzopinakor μ, Figure 2 is
The figure shows the infrared absorption spectrum μ of the inclusion complex obtained from penzovinacor μ and dimethylformamide. FIG. 3 shows the change over time in the amount of dimethylformamide released when a clathrate consisting of di-μ or monool and dimethylformamide is heated at 70° C. under normal pressure.
Claims (1)
とからなる分子包接錯体であつて、該分子包接錯体にお
けるジオールまたはモノオールのＯＨ基の伸縮振動に帰
属される赤外吸収スペクトルの少なくともひとつの吸収
ピーク位置が、ジオールまたはモノオールのＯＨ基の伸
縮振動に帰属される赤外吸収スペクトルの吸収ピーク位
置に対して１００〜２３０ｃｍ＾−＾１低波数側に移動
してなることを特徴とする分子包接錯体。 ２、ジオールまたはモノオールのＯＨ基の伸縮振動に帰
属される赤外吸収スペクトルの吸収ピーク位置に対して
、１００〜２３０ｃｍ＾−＾１低波数側に移動した位置
にＯＨ基の吸収ピークを少なくともひとつ有するジメチ
ルホルムアミドとジオールまたはモノオールとからなる
分子包接錯体を利用する溶剤分離方法であつて、該分子
包接錯体を形成しうるジオールまたはモノオールをジメ
チルホルムアミド含有液と接触させて分子包接錯体を形
成し、続いて該分子包接錯体を該ジメチルホルムアミド
含有液から分離回収し、更に該分子包接錯体からジメチ
ルホルムアミドを脱離させることを特徴とする溶剤分離
方法。[Scope of Claims] 1. A molecular inclusion complex consisting of dimethylformamide and a diol or monool, the infrared absorption spectrum being attributed to the stretching vibration of the OH group of the diol or monool in the molecular inclusion complex. The position of at least one absorption peak of is shifted to the lower wave number side by 100 to 230 cm^-^1 with respect to the absorption peak position of the infrared absorption spectrum attributed to the stretching vibration of the OH group of the diol or monool. A molecular inclusion complex characterized by: 2. At least the absorption peak of the OH group is located at a position 100 to 230 cm^-^1 lower than the absorption peak position of the infrared absorption spectrum attributed to the stretching vibration of the OH group of the diol or monool. A solvent separation method that utilizes a molecular inclusion complex consisting of dimethylformamide and a diol or monool, in which the diol or monool capable of forming the molecular inclusion complex is brought into contact with a dimethylformamide-containing liquid to separate the molecular inclusion complex. A method for solvent separation, which comprises forming a clathrate complex, subsequently separating and recovering the molecular clathrate complex from the dimethylformamide-containing liquid, and further eliminating dimethylformamide from the molecular clathrate complex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4242686A JPS62198651A (en) | 1986-02-27 | 1986-02-27 | Hydrogen-bonding molecular clathrate complex and separation of solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4242686A JPS62198651A (en) | 1986-02-27 | 1986-02-27 | Hydrogen-bonding molecular clathrate complex and separation of solvent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62198651A true JPS62198651A (en) | 1987-09-02 |
Family
ID=12635734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4242686A Pending JPS62198651A (en) | 1986-02-27 | 1986-02-27 | Hydrogen-bonding molecular clathrate complex and separation of solvent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62198651A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10370398B2 (en) | 2016-06-23 | 2019-08-06 | Tate & Lyle Technology Limited | Liquid-liquid extraction of DMF |
-
1986
- 1986-02-27 JP JP4242686A patent/JPS62198651A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10370398B2 (en) | 2016-06-23 | 2019-08-06 | Tate & Lyle Technology Limited | Liquid-liquid extraction of DMF |
| US10899783B2 (en) | 2016-06-23 | 2021-01-26 | Tate & Lyle Technology Limited | Liquid-liquid extraction of DMF |
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