JPH0324402B2 - - Google Patents
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- Publication number
- JPH0324402B2 JPH0324402B2 JP60014506A JP1450685A JPH0324402B2 JP H0324402 B2 JPH0324402 B2 JP H0324402B2 JP 60014506 A JP60014506 A JP 60014506A JP 1450685 A JP1450685 A JP 1450685A JP H0324402 B2 JPH0324402 B2 JP H0324402B2
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- Prior art keywords
- oxygen
- schiff base
- polar solvent
- complex
- cobalt complex
- 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.)
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- Gas Separation By Absorption (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Description
【発明の詳細な説明】
本発明はシツフ塩基コバルト錯体の酸素吸脱着
剤としての使用方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the use of Schiff base cobalt complexes as oxygen adsorbing and desorbing agents.
従来、酸素分子を可逆的に吸脱着するヘモグロ
ビンやミオグロビンのような生体における酸素運
搬体と類似の酸素吸脱着能を有する化合物を合成
しようという試みがなされており、ポルフイリン
錯体（J.P.Collman et.al.J.of Am.Chem.Soc.97
1427（1975）等）、Co（salen）錯体（M.Calvin
et.al.of Am.Soc.68 2254（1946）等）等いくつか
の酸素吸脱着剤が知られている。しかしながら、
これら従来の酸素吸脱着剤は(1)複核錯体生成に伴
う不可逆的な酸化劣化が起こりやすい、(2)少量の
水分の存在によつて酸化劣化が起こりやすい、(3)
室温付近での酸素吸着効率が悪い等の欠点を有し
ていた。 Previous attempts have been made to synthesize compounds that have oxygen adsorption and desorption abilities similar to those of biological oxygen carriers such as hemoglobin and myoglobin, which reversibly adsorb and desorb oxygen molecules. J.of Am.Chem.Soc.97
1427 (1975) etc.), Co(salen) complex (M.Calvin
et.al. of Am. Soc. 68 2254 (1946), etc.) Some oxygen adsorbing and desorbing agents are known. however,
These conventional oxygen adsorbing and desorbing agents (1) are susceptible to irreversible oxidative deterioration due to the formation of dinuclear complexes, (2) are susceptible to oxidative deterioration in the presence of small amounts of moisture, and (3)
It had drawbacks such as poor oxygen adsorption efficiency near room temperature.
又、H.Diehl et.al Iowa State Coll.J.Sci22
91（1947）には、水溶液中での３−及び４−位ヒ
ドロキシ誘導体の合成法ならびにそれらの酸素吸
収能が報告されているが、いずれも酸素吸収能は
ないとされている。 Also, H.Diehl et.al Iowa State Coll.J.Sci22
91 (1947) reports a method for synthesizing 3- and 4-position hydroxy derivatives in an aqueous solution and their oxygen absorption ability, but it is said that none of them have oxygen absorption ability.
本発明者はかかる欠点のない、室温・常圧のお
だやかな条件の下で効率よく酸素を吸収し、可逆
的に吸脱着を行う酸素吸脱着剤を提供するために
鋭意検討した結果、従来酸素吸収能がないとされ
ていた、例えば上記の如き特定のシツフ塩基コバ
ルト錯体を
(a) 極性溶媒中で又は
(b) 極性溶媒中で処理することにより極性溶媒の
配位結合体を形成した後極性溶媒の脱離処理を
行つた後使用すること
により当該錯体に酸素吸収能を発現せしめること
ができることを見出し本発明に到達した。すなわ
ち本発明は、
一般式
〔ここで水酸基の置換位置は３−，４−，５−，
６−位のいずれかであることを示す。〕
で示されるシツフ塩基コバルト錯体を
(a) 非プロトン性極性溶媒に接触させた状態で、
或いは
(b) 非プロトン性極性溶媒に接触させた後、当該
溶媒を脱離させた状態で
用いることを特徴とするシツフ塩基コバルト錯体
の酸素吸脱着剤としての使用方法である。 As a result of intensive studies to provide an oxygen adsorbent/desorbent that does not have these drawbacks, efficiently absorbs oxygen under mild conditions of room temperature and normal pressure, and reversibly adsorbs and desorbs oxygen, After forming a polar solvent coordination complex by treating certain Schiff base cobalt complexes, such as those mentioned above, which were said to have no absorption capacity, (a) in a polar solvent or (b) in a polar solvent. The present invention has been achieved by discovering that the complex can be made to exhibit oxygen absorption ability by using the complex after it has been subjected to removal treatment of the polar solvent. That is, the present invention has the general formula [Here, the substitution positions of the hydroxyl group are 3-, 4-, 5-,
Indicates any of the 6-positions. ] The Schiff base cobalt complex represented by (a) is brought into contact with an aprotic polar solvent,
Alternatively, (b) a method of using a Schiff base cobalt complex as an oxygen adsorption/desorption agent, which is characterized in that the Schiff base cobalt complex is used in a state in which it is brought into contact with an aprotic polar solvent and then the solvent is removed.
従来、酸素吸収能がないとされていたシツフ塩
基コバルト錯体のヒドロキシ誘導体を本発明の方
法に従い活性化された状態で用いることにより酸
素吸収能を発現せしめることが可能となつた。 By using the hydroxy derivative of the Schiff base cobalt complex, which was conventionally thought to have no oxygen absorption ability, in an activated state according to the method of the present invention, it has become possible to develop oxygen absorption ability.
本発明で用いられるシツフ塩基コバルト錯体は
低原子価状態にあるコバルトとシツフ塩基化合物
からなる配位子との錯体であつてシツフ塩基化合
物からなる配位子はビスサリチルアルデヒドエチ
レンジイミン（サレン）骨格を有するヒドロキシ
誘導体である。一般式（）における水酸基の置
換位置は３−，４−，５−，６−位のいずれかで
ある。 The Schiff base cobalt complex used in the present invention is a complex of cobalt in a low valence state and a ligand consisting of a Schiff base compound, and the ligand consisting of a Schiff base compound is bissalicylaldehyde ethylenediimine (salen). It is a hydroxy derivative with a skeleton. The substitution position of the hydroxyl group in the general formula () is any of the 3-, 4-, 5-, and 6-positions.
本発明で用いられるシツフ塩基コバルト錯体は
ジヒドロキシベンズアルデヒドとエチレンジアミ
ンを反応させてシツフ塩基を調製し、これに低原
子価コバルトを導入することにより得られる。 The Schiff base cobalt complex used in the present invention can be obtained by reacting dihydroxybenzaldehyde with ethylenediamine to prepare Schiff base, and introducing low-valent cobalt into this.
本発明で用いられる非プロトン性極性溶媒とは
シツフ塩基コバルト錯体の軸配位座に配位可能な
化合物であつて、例えばピリジンおよびその誘導
体、イミダゾール及びその誘導体、ジメチルホル
ムアミド、ジメチルスルホキシド、ヘキサメチル
ホスホリツクトリアミド等である。該シツフ塩基
コバルト錯体を(a)かかる極性溶媒中に溶解あるい
は分散し、必要に応じ加熱することにより極性溶
媒の配位結合体を形成させ、これをそのまま用い
ても良く、更には次いで、例えば、減圧下で脱気
する、あるいは窒素雰囲気下で還流することによ
り可逆的な酸素吸収能を有する活性化された酸素
吸脱着剤を得ることができる。また、(b)極性溶媒
の配位結合体を形成させた後、極性溶媒を除去あ
るいは脱離することによつても可逆的な酸素吸収
能を有する活性化された酸素吸脱着剤が得られ
る。 The aprotic polar solvent used in the present invention is a compound capable of coordinating to the axial coordinate site of the Schiff base cobalt complex, such as pyridine and its derivatives, imidazole and its derivatives, dimethylformamide, dimethyl sulfoxide, hexamethyl These include phosphoric triamide. The Schiff base cobalt complex may be (a) dissolved or dispersed in such a polar solvent and heated if necessary to form a coordination bond of the polar solvent, and this may be used as it is, or further, for example, An activated oxygen adsorbing/desorbing agent having reversible oxygen absorption ability can be obtained by degassing under reduced pressure or refluxing under a nitrogen atmosphere. Furthermore, (b) an activated oxygen adsorbing/desorbing agent having reversible oxygen absorption ability can be obtained by forming a coordination bond of a polar solvent and then removing or desorbing the polar solvent. .
このようにして得られた、活性化された酸素吸
脱着剤は粉末固体状態あるいはジメチルホルムア
ミド、ジメチルスルホキシド、ピリジン、イミダ
ゾール、ヘキサメチルホスホリツクトリアミド等
を溶媒とする溶液またはサスペンジヨン状態とし
てこれを酸素と接触させると室温・常圧下で速や
かに酸素を吸着する。また酸素を吸着した酸素吸
着剤を減圧下におき必要に応じて加熱するか、あ
るいは溶媒の還流温度に保てば吸着されていた酸
素は容易に脱着される。以下実施例を挙げて本発
明をさらに説明するが本発明はこれらに限定され
るものではない。 The activated oxygen adsorbing and desorbing agent obtained in this manner can be prepared in a powder solid state or in a solution or suspension state using dimethylformamide, dimethyl sulfoxide, pyridine, imidazole, hexamethylphosphoric triamide, etc. as a solvent. When brought into contact with oxygen, it quickly adsorbs oxygen at room temperature and normal pressure. Further, if the oxygen adsorbent that has adsorbed oxygen is placed under reduced pressure and heated if necessary, or maintained at the reflux temperature of the solvent, the adsorbed oxygen can be easily desorbed. The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.
実施例 １
２，４−ジヒドロキシベンズアルデヒド11.1ｇ
をイソプロパノール200mlに溶解し、これにエチ
レンジアミン2.4ｇをイソプロパノール200mlに溶
かした溶液を滴下した。撹拌しながら2.5時間還
流して反応させた。放冷後、メタノール80mlに溶
解した水酸化カリウム4.5ｇを加えた。次いで酢
酸コバルト４水塩10ｇを45mlの水に溶かした溶液
を加え2.5時間還流して反応させた。一晩放冷後
生じた沈澱を別し暗赤色針状結晶を得た。得ら
れた結晶をジメチルホルムアミドに一旦加熱溶解
した後徐冷すると赤褐色の針状結晶が得られた。Example 1 2,4-dihydroxybenzaldehyde 11.1g
was dissolved in 200 ml of isopropanol, and a solution of 2.4 g of ethylenediamine dissolved in 200 ml of isopropanol was added dropwise thereto. The mixture was refluxed and reacted for 2.5 hours while stirring. After cooling, 4.5 g of potassium hydroxide dissolved in 80 ml of methanol was added. Next, a solution of 10 g of cobalt acetate tetrahydrate dissolved in 45 ml of water was added, and the mixture was refluxed for 2.5 hours to react. After cooling overnight, the resulting precipitate was separated to obtain dark red needle-like crystals. The obtained crystals were once heated and dissolved in dimethylformamide and then slowly cooled to obtain reddish brown needle-shaped crystals.
かくして得られた生成物の固定を行つたとこ
ろ、IR測定により1530cm-1付近にνC＝Ｎの吸収
が認められシツフ塩基の生成が確認された。また
元素分析より生成物の組成比がＣ：Ｈ：Ｎ：Co
＝50.2：4.0：7.2：15.2（％）と得られ、計算値
（C16H14N2O4Co…O2、Ｃ：Ｈ：Ｎ：Co＝49.4：
3.6：7.2：15.1（％））に一致した。 When the product thus obtained was fixed, an absorption of νC=N was observed near 1530 cm -1 by IR measurement, confirming the formation of Schiff's base. Also, elemental analysis revealed that the composition ratio of the product was C:H:N:Co.
= 50.2: 4.0: 7.2: 15.2 (%) was obtained, and the calculated value (C 16 H 14 N 2 O 4 Co...O 2 , C: H: N: Co = 49.4:
3.6:7.2:15.1 (%)).
このようにして得たシツフ塩基コバルト錯体
1.06ｇを試料フラスコに秤取し、160℃に加熱し
て２時間真空脱気した。これを30℃の恒温槽内の
ガスビユレツトに取付け大気圧の酸素に接触させ
た所90分で19.8ml、145分で78.6mlの酸素を吸着
した。 Schiff base cobalt complex thus obtained
1.06 g was weighed into a sample flask, heated to 160°C, and vacuum degassed for 2 hours. When this was attached to a gas bottle in a constant temperature bath at 30°C and brought into contact with oxygen at atmospheric pressure, it adsorbed 19.8 ml of oxygen in 90 minutes and 78.6 ml in 145 minutes.
実施例 ２
実施例１で得たシツフ塩基コバルト錯体0.0985
ｇをジメチルホルムアミド50mlに溶解し、凍結脱
気した。30℃恒温槽内のガスビユレツトに取付け
大気圧の酸素に接触させた所９分で13.7ml、19分
で15.1mlときわめて速い酸素吸収が認められ、約
１時間で飽和に達し15.9mlの酸素を吸収した。Example 2 Schiff base cobalt complex obtained in Example 1 0.0985
g was dissolved in 50 ml of dimethylformamide and freeze-degassed. When attached to a gas bottle in a 30°C constant temperature oven and exposed to atmospheric pressure oxygen, extremely fast oxygen absorption was observed: 13.7ml in 9 minutes and 15.1ml in 19 minutes, reaching saturation in about 1 hour and absorbing 15.9ml of oxygen. Absorbed.
比較例 １
実施例２においてシツフ塩基コバルト錯体を加
えない他は全く同様の操作を行い酸素吸収を測定
した。９分で5.0ml、19分で6.0mlの酸素を吸収
し、これ以降は酸素吸収量の増加は認められなか
つた。Comparative Example 1 The same procedure as in Example 2 was performed except that the Schiff base cobalt complex was not added, and oxygen absorption was measured. 5.0 ml of oxygen was absorbed in 9 minutes and 6.0 ml in 19 minutes, and no increase in the amount of oxygen absorbed was observed after this point.
実施例 ３
実施例１で得たシツフ塩基コバルト錯体0.0985
ｇをジメチルホルムアミド50mlに溶解し、凍結脱
気した。30℃恒温槽内のガスビユレツトに取付け
大気圧の酸素に接触させた所97分で101.5ml／ｇ
の酸素を吸収した。この錯体のジメチルホルムア
ミド溶液を窒素気流下で１時間還流した後凍結脱
気し、再び酸素吸収を測定した。133分で93.4
ml／ｇの酸素を吸収した。Example 3 Schiff base cobalt complex obtained in Example 1 0.0985
g was dissolved in 50 ml of dimethylformamide and freeze-degassed. 101.5ml/g after 97 minutes when attached to a gas bottle in a 30℃ constant temperature oven and exposed to atmospheric pressure oxygen
absorbed oxygen. A dimethylformamide solution of this complex was refluxed for 1 hour under a nitrogen stream, then frozen and degassed, and oxygen absorption was measured again. 93.4 in 133 minutes
Absorbed ml/g of oxygen.
比較例 ２
実施例３において実施例１の錯体にかえてＮ，
N′−エチレンビス（サリシリデンイミナイト）
コバルトを用いる他は同様にして酸素吸脱着能を
調べた。97分で34.6ml／ｇの酸素を吸収した。実
施例３と同様に脱気後再び酸素吸収を測定した
所、34.0ml／ｇであつた。Comparative Example 2 In Example 3, instead of the complex of Example 1, N,
N′-ethylenebis(salicylidene iminite)
Oxygen adsorption/desorption ability was investigated in the same manner except that cobalt was used. Absorbed 34.6 ml/g of oxygen in 97 minutes. After degassing, oxygen absorption was measured again in the same manner as in Example 3, and it was found to be 34.0 ml/g.
比較例 ３
２，４−ジキドロキシベンズアルデヒト11.1ｇ
をイソプロパノール200mlに溶解し、これにエチ
レンジアミン2.4ｇをイソプロパノール200mlに溶
かした溶液を滴下した。撹拌しながら2.5時間還
流して反応させた。放冷後析出したシツフ塩基の
黄色結晶を別した。Comparative example 3 2,4-dihydroxybenzaldehyde 11.1g
was dissolved in 200 ml of isopropanol, and a solution of 2.4 g of ethylenediamine dissolved in 200 ml of isopropanol was added dropwise thereto. The mixture was refluxed and reacted for 2.5 hours while stirring. After cooling, yellow crystals of Schiff's base precipitated were separated.
得られたシツフ塩基6.0ｇと水酸化ナトリウム
1.6ｇを100mlの水に溶解し、4.8ｇの塩化コバル
トを加えた後2.5時間還流して反応させた。沈澱
したこげ茶色の錯体を別し、水洗して100℃で
４時間真空乾燥した。 6.0 g of Schiff's base obtained and sodium hydroxide
1.6 g was dissolved in 100 ml of water, 4.8 g of cobalt chloride was added, and the mixture was refluxed for 2.5 hours to react. The precipitated dark brown complex was separated, washed with water, and vacuum dried at 100°C for 4 hours.
このようにして得たシツフ塩基コバルト錯体
1.06ｇを試料フラスコに秤取し、160℃で２時間
脱気した。これを30℃の恒温槽内のガスビユレツ
トに取り付け大気圧の酸素に接触させたが、酸素
の吸収はみられなかつた。 Schiff base cobalt complex thus obtained
1.06g was weighed into a sample flask and degassed at 160°C for 2 hours. This was placed in a gas bottle in a constant temperature oven at 30°C and brought into contact with oxygen at atmospheric pressure, but no oxygen absorption was observed.
Claims (1)
６−位のいずれかであることを示す。〕 で表わされるシツフ塩基コバルト錯体を (a) 非プロトン性極性溶媒に接触させた状態で、
或いは (b) 非プロトン性極性溶媒に接触させた後、当該
溶媒を脱離させた状態で 用いることを特徴とするシツフ塩基コバルト錯体
の酸素吸脱着剤としての使用方法。[Claims] 1 General formula () [Here, the substitution positions of the hydroxyl group are 3-, 4-, 5-,
Indicates any of the 6-positions. ] A Schiff base cobalt complex represented by (a) is brought into contact with an aprotic polar solvent,
or (b) a method for using a Schiff base cobalt complex as an oxygen adsorbing/desorbing agent, which comprises contacting with an aprotic polar solvent and then using it in a state in which the solvent is removed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60014506A JPS61174286A (en) | 1985-01-30 | 1985-01-30 | Use of shiff base-cobalt complex as oxygen adsorbent and desorption agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60014506A JPS61174286A (en) | 1985-01-30 | 1985-01-30 | Use of shiff base-cobalt complex as oxygen adsorbent and desorption agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61174286A JPS61174286A (en) | 1986-08-05 |
| JPH0324402B2 true JPH0324402B2 (en) | 1991-04-03 |
Family
ID=11862950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60014506A Granted JPS61174286A (en) | 1985-01-30 | 1985-01-30 | Use of shiff base-cobalt complex as oxygen adsorbent and desorption agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61174286A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0248014A (en) * | 1988-08-05 | 1990-02-16 | Agency Of Ind Science & Technol | Separation of gaseous mixture |
| CN102924488B (en) * | 2012-08-30 | 2016-02-10 | 齐鲁工业大学 | The pyrazine west not structure of alkali title complex, preparation and the purposes of one class argentiferous |
| CN103073510B (en) * | 2013-03-01 | 2014-12-17 | 齐鲁工业大学 | Structure, preparation and application of new pyrazinyl schiff base compound |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS594439A (en) * | 1982-06-30 | 1984-01-11 | Nippon Sanso Kk | Purifying method of inert gas |
-
1985
- 1985-01-30 JP JP60014506A patent/JPS61174286A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61174286A (en) | 1986-08-05 |
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