JPH02191545A - Oxygen absorbing and desorbing agent and its production - Google Patents

Abstract

PURPOSE:To produce the oxygen adsorbing and desorbing agent by which high- purity oxygen is obtained in good yield by dispersing and fixing an axial ligand in a porous high polymer resin by ionic bonding or covalent bonding, coordinate- bonding a complex having oxygen adsorptivity to the axial ligand. CONSTITUTION:An axial ligand to which a complex having adsorptivity can be coordinate-bonded is previously introduced into a porous high polymer resin, dispersed and fixed by ionic bonding or covalent bonding. The complex having oxygen adsorptivity is then coordinate-bonded to the axial ligand introduced into the high polymer resin to produce an oxygen adsorbent. Pyridine, imidazole, an alkylamine, etc., are exemplified as the axial ligand. Meanwhile, a compd shown by formula I is appropriately used as the complex having oxygen adsorptivity (R<1>, R<2> and R<3> are H, an alkoxy group, etc., R<4> is H, a methyl group, etc., R<5>, R<6>, R<7> and R<8> are an alkyl group, a phenyl group, etc.).

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an oxygen adsorbent/desorbent and a method for producing the same, and in particular to an adsorbent for separating oxygen from the air by an adsorption method such as a pressure or temperature fluctuation method. The present invention relates to an oxygen adsorbing/desorbing agent suitable as an oxygen adsorbing/desorbing agent and a method for producing the same.

[Conventional technology]

When separating and collecting oxygen from the air, a pressure fluctuation air separation method (P
S A) or temperature variable air separation method (T S
A) is known. As the adsorption/desorption agent, natural or synthetic zeolites which preferentially adsorb nitrogen, carbon molecular sieves which adsorb oxygen faster than nitrogen, and improved versions thereof are used.

[Problem to be solved by the invention]

However, in the above-mentioned methods, since both oxygen and nitrogen are adsorbed, it is difficult to obtain high-purity oxygen, and the yield has to be sacrificed in order to obtain high-purity oxygen.

Furthermore, various complexes are known as having oxygen adsorption ability, but these typically do not react with oxygen unless the temperature is below room temperature, and they also have the problem of deteriorating in a solution state.

Therefore, the present invention reversibly reacts only with oxygen at room temperature, does not deteriorate even after repeated use, and produces high purity oxygen in high yield.
Another object of the present invention is to provide an oxygen adsorbing/desorbing agent that can be obtained with low power consumption and a method for producing the same.

[Means to solve the problem]

In order to achieve the above object, the oxygen adsorbing/desorbing agent of the present invention has an axial ligand dispersed and fixed in a porous polymer resin by ionic or covalent bonds, and the axial ligand has oxygen adsorption ability. In particular, the axial ligand is an axial ligand that increases the oxygen adsorption ability of the complex by coordinating with a complex having oxygen adsorption ability. It is characterized by:

Further, in the method for producing an oxygen adsorbing/desorbing agent of the present invention, in producing the oxygen adsorbing/desorbing agent by dispersing and fixing a complex having oxygen adsorbing ability in a porous polymer resin, firstly, the complex is coordinated. A bondable axial ligand is introduced in advance into the porous polymer resin by ionic bonding or covalent bonding, and is dispersed and fixed therein, and then the complex is coordinately bonded to the axial ligand, and a second A porous polymer resin in which the axial ligands are dispersed and fixed is heated to 70 to 130 in which the complex is dissolved in a polar solvent
℃ immersed in a complex solution to form a coordinate bond between the complex and the axial ligand, and thirdly, the axial ligand dispersed and fixed in the porous polymer resin is immersed in the complex. After the coordinate bonding, the complex physically adsorbed to the porous polymer resin is removed, and the fourth step is to remove the axial ligand to which the complex can be coordinately bonded to the porous polymer resin by ionic bonding or covalent bonding. The porous polymer resin in which the axial ligands are dispersed and fixed is then immersed in a complex solution in which a complex having oxygen adsorption ability is dissolved in a polar solvent. death,
By heating the complex solution to a temperature of 70 to 130'C to swell the porous polymer resin, the complex and the axial ligand are coordinately bonded, and then the polar solvent and the porous polymer resin are bonded together. This method is characterized by removing complexes that are physically adsorbed on high-quality polymer resins.

The porous polymer resin described above is used as a carrier for immobilizing a complex that selectively adsorbs and desorbs oxygen.

Further, the above-mentioned axial ligand is used to enhance the oxygen adsorption ability of the complex, but at the same time, it also plays a role as a chain for fixing the complex to the above-mentioned porous polymer resin.

Various types of these can be used depending on the bond structure between the porous polymer resin and the axial ligand.

First, the above-mentioned axial ligands include pyridine, imidazole,
Alkylamines or derivatives thereof, which have ionic bonds or functional groups such as vinyl groups, are used.

This functional group is necessary for dispersing and fixing the axial ligand in the porous polymer resin, and examples of the axial ligand having an ionic bond as a functional group include, for example, 3-methyl-1,1 ' -Dodecyldiimidazolium iodide; 1-(3-aminopropyl)imidazole hydrochloride; 4-
Sodium pyridinethanesulfonate; 4-picolylamine hydrochloride: etc. can be mentioned.

In these axial ligands having ionic bonds, the lone pair of electrons of the nitrogen atom of the imidazole or pyridine group is donated to the central metal of the complex, so that the complex is coordinated. When the nitrogen atom is close to the atom, the electron pair donating property of the nitrogen atom is weakened. As a result, the oxygen adsorption ability of the complex may also be weakened, so a structure having at least one alkyl carbon between the imidazole or pyridine ionic bonding moiety is preferable, and more preferably three alkyl carbons. As described above, the most preferable structure is one in which the number of alkyl carbon atoms is 10 or more.

Examples of the axial ligand having a vinyl group as a functional group include 4-vinylpyridine: 8-(imidazol-1-yl)octatool.1-
Vinyl imidazolnia and the like can be mentioned.

Examples of the axial ligand having a hydroxyl group as a functional group include 4-(imidazol-1 yl)phenol; and the like.

Examples of the axial ligand having an amine as a functional group include 1-(3-aminopropyl)imidazole; 4-aminopyridine; 3-pyridinepropanol; and the like.

Next, various resins can be used as the porous polymer resin. For example, as a porous polymer resin that disperses and fixes an axial ligand having an ionic bond as a functional group,
Various ion exchange resins can be used.

For example, when an imidazole group or a pyridine group is present in the cation moiety, as in the case of 1-(3-aminopropyl)imidazole hydrochloride, a cation exchange resin is used, as in the case of the above-mentioned sodium 4-pyridinethanesulfonate, When a pyridine group or an imidazole group is present in the anion portion, an anion exchange resin is used.

In addition, when using a cation exchange resin, it is desirable to use one in which the functional group of the cation exchange resin is sodium type. At this time, if a cation exchange resin in which the functional group of the resin is of the proton type is used, there is a possibility that the protons remaining in the resin after the reaction react with the complex and deteriorate the complex. Therefore, when using a proton type cation exchange resin, Na
It is desirable to perform ion exchange with a cation such as + to convert it into a cation type other than proton.

Further, in the case of the above-mentioned 4-vinylpyridine where the functional group of the axial ligand is a vinyl group, it is fixed by a covalent bond. For example, by reacting an axial ligand having a vinyl group with a monomer such as styrene to synthesize a copolymer, a porous polymer resin in which the axial ligand is dispersed and fixed can be obtained. This synthesis can be easily carried out according to conventional methods, but in addition to crosslinking agents such as divinylbenzene and polymerization initiators such as azobisisobutyronitrile, dispersion/suspension stabilizers such as polyvinyl alcohol, amyl alcohol, etc. It is necessary to add a polymer precipitant such as

As the porous polymer resin for dispersing and fixing the axial ligand having a hydroxyl group or amine as a functional group, a cation exchange resin having a sulfone group can be used. Treatment of this type of resin with, for example, phosphorus pentachloride converts the sulfone groups to sulfonyl chloride according to the following formula.

PCl5 / POCl2 R-3o, HR-3o2C (In the above formula, R represents a resin.) This sulfonyl chloride easily reacts with a hydroxyl group or an amine, so this reaction exchanges the axial ligand with the above cation. It can be dispersed and fixed in resin. For example, in the case of the above-mentioned 8-(imidazol-1-yl)octatool, it is fixed by the reaction of the following formula.

(In the above formula, R represents a resin.) In the case of the above 1-(3-aminopropyl)imidazole, it is fixed by the reaction of the following formula.

Any type of porous polymer resin can be used as long as it has a functional group that can react with the functional group contained in the porous polymer resin.

In this manner, a complex having oxygen adsorption ability is coordinately bonded to the axial ligand of the axial ligand-containing porous polymer resin in which the axial ligand has been dispersed and fixed in advance, and is dispersed and fixed within the resin.

As this complex having oxygen adsorption ability, what is generally known as an oxygen carrier can be used, and it can coordinately bond with the axial ligand of the above-mentioned axial ligand-containing porous polymer resin. Select a material that reversibly adsorbs and desorbs oxygen at room temperature and near normal pressure. The complex having the oxygen adsorption ability of this plate includes, for example, the general formula: (In the above formula, R represents a resin). R2 and R3 each represent hydrogen or an alkoxy group such as OCU, an alkyl group such as CH, or a phenyl group, R4 represents hydrogen, a methyl group, or a phenyl group, R5 R6, R?, and R8 each represent hydrogen or CH3 (In the above formula, RI and R2 each represent hydrogen, a methyl group, or a phenyl group.) or a complex represented by the general formula; Formula; (In the above formula, RI represents hydrogen or a phenyl group, R2
represents hydrogen or an alkyl group such as CH3. ) Complexes represented by the following can be mentioned.

All of these complexes have a 4-coordinate structure, and usually have a 6-coordinate structure.
It has a stable coordination structure. Therefore, when the axial ligand is coordinated to the fifth coordination site of this complex,
The oxygen adsorption capacity of the sixth coordination site increases and oxygen is adsorbed here.

Generally, any type of complex can be used as long as it exhibits oxygen adsorption ability when the axial ligand is coordinated to the fifth coordination site. It is preferable to use one having a solubility in a polar solvent described below of 0.1 M or more. Specifically, (N,N'-bis(4-methoxysalicylaldehyde)dimethylethylenediamine)cobalt; or (N,N'-bis(4-methoxysalicylaldehyde)tetramethylethylenediamine)cobalt; Ligand and complex It is necessary to bring them closer together. Therefore, it is necessary to make the complex movable in the porous polymer resin so that it comes into contact with the axial ligand in the resin.

The contact between the two can be carried out by dissolving the complex in a polar solvent to prepare a complex solution, immersing the axial ligand-containing porous polymer resin in the complex solution, and dipping the complex solution at 50%
This can be carried out by heating the porous polymer resin to a temperature of ~150°C, preferably 70~130°C to swell the porous polymer resin.

This allows the complex to move within the resin, allowing for coordination bonding between the axial ligand fixed within the resin and the complex.

Examples of the above polar solvent include γ-butyrolactone; etc. can be raised.

In order to coordinately bond the complex and the axial ligand, the axial H, C-5-C, which is dispersed and fixed in the porous polymer resin.
H.

Dimethylformamide; (CH3) 2 N CH0 1-methyl-2-pyrrolidinone (N-methylpyrrolidinone); sulfolane; etc., but in order to reduce the evaporation loss of the polar solvent during heating, It is preferable to use a high-quality one.

Furthermore, since the complex solution is heated, the oxygen dissolved in the complex solution causes a trimerization reaction of the complex, which may deactivate the oxygen adsorption ability of the complex. Therefore, when the axial ligand-containing porous polymer resin is immersed in a complex solution and heated, it is preferable to make the solution anoxic by bubbling an inert gas such as argon gas.

At this time, if the heating temperature of the complex solution is less than 70°C, the swelling of the porous polymer resin will be insufficient and it will be difficult to make sufficient coordination bonds between the axial ligand and the complex. If the temperature exceeds 130° C., the complex may be decomposed, the polar solvent may be evaporated, and the energy of the heating source may be wasted.

As described above, the oxygen adsorbing/desorbing agent of the present invention can be obtained by heating the complex solution to form a coordinate bond between the axial ligand in the porous polymer resin and the complex. , the complex that is not coordinated to the axial ligand remains in the porous polymer resin due to physical adsorption. This complex that cannot be coordinated not only has a weak oxygen adsorption ability, but also inhibits the movement and diffusion of oxygen within the oxygen adsorbent and desorbent during oxygen adsorption and separation, reducing the performance of the oxygen adsorbing and desorbing agent. There is a risk that it may deteriorate.

Therefore, after performing the coordination bond, it is preferable to remove the complex remaining in the porous polymer resin by physical adsorption. This complex can be removed by separating the obtained oxygen adsorbing/desorbing agent from the complex solution and washing it with an appropriate solvent such as acetone.

Then, by drying the oxygen adsorbent/desorbent after washing by vacuum drying, etc., the polar solvent contained in the oxygen adsorbent/desorbent and the cleaning solvent mentioned above are removed, and the swollen resin returns to its original state. It is possible to obtain an oxygen adsorbing/desorbing agent in which a complex that shrinks and has oxygen adsorption ability is dispersed and fixed in a porous polymer resin.

The axial ligands, porous polymer resins, and complexes containing these functional groups are listed as examples and do not limit the scope of the present invention, and various types can be used depending on the conditions.

[For production]

When the exemplified complex is alone in solution, the temperature is 25°C.
At around room temperature, it usually does not exhibit enough oxygen adsorption ability to separate oxygen. Additionally, a degradation known as trimerization occurs.

However, in the oxygen adsorbing/desorbing agent of the present invention, since the complex is dispersed and fixed in the polymer resin, the thermal vibration of the complex is suppressed, and as a result, the complex is placed at a low temperature, and even at room temperature, oxygen Shows sufficient oxygen adsorption capacity for separation. Furthermore, since it is dispersed and fixed, trimerization reaction is prevented and deterioration of the complex is eliminated.

This oxygen adsorbing/desorbing agent easily desorbs and releases oxygen by heating or reducing pressure after adsorbing oxygen, and can adsorb and desorb oxygen repeatedly.

〔Example〕

Hereinafter, the present invention will be explained in more detail based on Examples and Comparative Examples.

Example 1 1.2-diamino-2-methylpropane; (CH3)2
To a solution of C(NH2)CH2NH24,41 g (0,05 mol) dissolved in 20 ml of ethanol at a temperature of 90°C, 15,22 g (0,05 mol) of 4-methoxysalicylaldehyde; CHO OCH3 was added and reacted to form bis. A yellow solution of (4-methoxysalicylaldehyde)dimethylethylenediamine was obtained.

To this, 12.45 g of cobalt acetate tetrahydrate (0°05
mol) was added to obtain a dark light colored precipitate. This is left to cool, filtered with suction, and then vacuum dried to form a complex with oxygen adsorption ability; (N,N'-bis(4-methoxysalicylaldehyde))
Cobalt (dimethylethylenediamine) (hereinafter referred to as Co(
23 g of 4-MeO5a 1) Dmen was obtained (
yield 85%).

Co(4-MeO3a l)Dme synthesized in this way
nd, 3z was dissolved in 10 ml of γ-butyrolactone,
0.072 times as a complex solution. 2 g (dry weight) of a porous copolymer granular resin with a diameter of approximately 1 mm+ is obtained by copolymerizing 4-vinylpyridine and styrene in this complex solution using a conventional method.
was immersed in an oxygen-free environment, heated to 90°C, and refluxed for 4 hours under an argon gas stream.

After cooling, the complex solution and resin are separated, the resin is washed with acetone to remove the physically adsorbed complex, and finally the resin is heated to 80°C.
Vacuum drying was carried out for 15 hours to obtain 1.7 g of an oxygen adsorption/desorption agent in which Co (4-Me OS a 1) Dmen was dispersed and fixed in a porous copolymer granular resin.

The amount of oxygen and nitrogen gas adsorbed in the obtained oxygen adsorbent/desorbent was measured gravimetrically using an electronic balance.

As a result, although the adsorption amount of nitrogen gas was so small that it could not be measured, the adsorption capacity shown in the figure for oxygen gas was obtained. still,
The porous copolymer granular resin made of 4-vinylpyridine and styrene does not have the ability to adsorb oxygen and nitrogen gas.

Comparative Example The same procedure as in Example 1 was performed except that the complex solution was treated at room temperature without heating. The adsorption capacity of the resulting resin for oxygen gas was extremely low.

Example 2 2,3-dimethyl-2,3-dinitrobutane: (CHi) 2 using tin C3C50O as a catalyst according to a conventional method.
C(NOx) C(CH3) 2 30g of N0
Tetramethylethylenediamine by treatment with 7% aqueous hydrochloric acid; (CH3)2 CCNH2)C(CH3)2 NH21
0.9 g was obtained (yield 55%).

This was reacted with 15.22 g of 4-methoxysalicylaldehyde and 12.45 g of cobalt acetate tetrahydrate in the same manner as in Example 1 to form a complex (
N,N'-bis(4-methoxysalicylaldehyde)tetramethylethylenediamine) cobalt (hereinafter referred to as Co(
17.6 g of 4-Messal)Tmen were obtained (yield: 80%).

Co (4-MeO8a 1)Tm synthesized in this way
enO, 88 g to 1-methyl-2-pyrrolidinone 5.0
ml to obtain a 0.40 g complex solution.

Hereinafter, Co (4-MeO3a l)Tmen was dispersed and fixed in 1 g (dry weight) of a granular resin of a porous copolymer of 4-vinylpyridine and styrene using the same procedure as in Example 1, and 0 .8g was obtained.

The amount of oxygen gas adsorbed and desorbed by the obtained oxygen adsorbent/desorbent was measured using an electronic balance. In this measurement, the temperature was changed from -20℃ to +5℃.
The temperature was varied between 0°C and the amount of oxygen adsorption and desorption based on temperature changes was measured.

As a result, when the oxygen partial pressure was 500 TorrO, the amount of oxygen adsorption and desorption was 0.811+g per gram of granular resin.

This temperature fluctuation type oxygen adsorption/desorption test was repeated 200 times, but the amount of oxygen adsorption/desorption did not change.

Example 3 First, 1,1'-dodecamethylene diimidazole was synthesized by a conventional method, and in a toluene solution (200 ml) of 227 g (7°50 x 10-3 mol) of this],]1'-dodecamethylene diimidazole, Iodomethane 5°38g (3
, 75 x 10-' mol) in toluene was added dropwise, and after reacting overnight at 50°C, the solid of 0.0% was filtered out.
Washed with toluene. Next, vacuum dry at 100°C.
3-methyl-1,1'-dodecyldiimidazolium iodide as an axial ligand 1.5. , Og was obtained (yield 9
0%).

On the other hand, a proton type cation exchange resin, trade name Amberlyst (15) (manufactured by Tokyo Organic Chemical Industry ■)], was ion-exchanged with 100 equivalents (176 g) of sodium hydroxide under distilled water to obtain a sodium form. A cation exchange resin was obtained. Next, 0.5 g of this sodium type cation exchange resin was ion-exchanged with 2.5 equivalents (3.47 g) of the 3-methyl-1,1' dodecyldiimidazolium iodide in distilled water. Measurement of the Na ion concentration of the filtrate revealed that the ion exchange rate was 48%.

Then, (Co(4-MeOS) synthesized in Example 2)
a1) 324g of Tmenl was dissolved in 10ml of 1-methyl-2-pyrrolidinone to prepare a 0.30M complex solution. In this complex solution, 0.5 g of the ion exchange resin into which the above-mentioned axial ligand was introduced was immersed under argon gas and heated to 100°C.
The mixture was refluxed for 3 days.

Hereinafter, in the same manner as in Example 1, Co (
4-MeOSa 1) An oxygen adsorption/desorption agent in which Tmen was embedded was obtained.

As a result of measuring the amount of oxygen gas adsorbed in the obtained oxygen adsorbing/desorbing agent, it was found that at an oxygen partial pressure of 300 Torr and an adsorption temperature of 25° C., 15.3 mg of oxygen was adsorbed per 1 g of resin.

Example 4 After drying 20 g of the cation exchange resin used in Example 3, it was poured into a mixed solvent of 125 g of phosphorus pentachloride/250 g of phosphorus oxychloride, and reacted under nitrogen at 100 to 110°C for 48 hours to form a sulfonyl chloride type resin. was converted into a cation exchange resin.

Next, 8-(imidazol-1-yl)octatool was synthesized by a conventional method, and the obtained 8-(imidazol-1-yl)
7 g of octatool) was dissolved in 1-methyl-2-pyrrolidinone, and the above sulfonyl chloride type resin 2. Og
8-
(imidazol-1-yl)octatool was dispersed and immobilized in the resin by covalent bonding.

Then, the complex Co(4-M e
OS a 1) T m e n 1-methyl-2
- A 0.3M solution of the complex was prepared by dissolving it in pyrrolidinone. In this solution, 2 g of the ion exchange resin in which the axial ligand was dispersed and fixed was immersed, and the mixture was soaked for 10 min in an argon gas atmosphere.
Reflux was carried out at 0°C for 24 hours.

Hereinafter, Co was added to the ion exchange resin in the same manner as in Example 1.
An oxygen adsorption/desorption agent in which (4-MeOSal)Tmen was embedded was obtained.

As a result of measuring the amount of oxygen gas adsorbed in the obtained oxygen adsorbing/desorbing agent, the oxygen partial pressure was 300 Torr, and the adsorption temperature was 25°C.
At this time, the amount of oxygen adsorbed was 7.62 mg per 1 g of resin.

〔Effect of the invention〕

As explained above, in the oxygen adsorbing and desorbing agent of the present invention, the complex that reversibly adsorbs and desorbs oxygen is dispersed and immobilized by coordinate bonding to the axial ligand that is dispersed and immobilized in the resin. A large amount of the complex can be retained in the resin, and the oxygen adsorption ability of the complex can be improved. Furthermore, since the complexes are each fixed to the axial ligands, the complexes are not degraded by the trimerization reaction of the complexes, and excellent oxygen adsorption ability can be maintained over a long period of time. Furthermore, since it adsorbs and desorbs only oxygen, by using it as an adsorbent for PSA or TSA, it is possible to obtain highly purified oxygen at a high yield, and the power unit consumption can be reduced.

In addition, when producing an oxygen adsorption/desorption agent, an axial ligand to which a complex can coordinate is dispersed and fixed in advance in a porous polymer resin, and a complex having oxygen adsorption ability is coordinated to the axial ligand. By bonding, a large amount of complex can be easily dispersed and fixed.

Furthermore, when coordinating a complex with oxygen adsorption ability to the axial ligand in the resin, the resin is immersed in a complex solution in which the complex is dissolved in a polar solvent, and the complex solution is heated.
Since the resin can be swollen and the complex can be moved into the interior of the resin, sufficient coordination bonding between the complex and the axial ligand can be achieved.

After dispersing and immobilizing the complex with oxygen adsorption ability through coordination bonds, this resin is washed to remove the complex that is physically adsorbed to the resin without coordination bonds. The movement and diffusion of oxygen can be made smoother, and the oxygen adsorption ability can be further improved.

[Brief explanation of the drawing]

The figure shows the oxygen adsorption ability of the oxygen adsorption/desorption agent produced in Example 1. O2 amount (mg/g) ■

Claims (1)

[Claims] 1. An axial ligand is dispersed and fixed in a porous polymer resin by ionic or covalent bonds, and a complex having oxygen adsorption ability is fixed to the axial ligand by coordinate bonds. An oxygen adsorbing and desorbing agent. 2. The oxygen adsorption/desorption method according to claim 1, wherein the axial ligand is an axial ligand that increases the oxygen adsorption ability of the complex by coordinating with the complex having oxygen adsorption ability. agent. 3. When manufacturing an oxygen adsorbing/desorbing agent by dispersing and fixing a complex having oxygen adsorption ability in a porous polymer resin, an axial ligand to which the complex can coordinate is preliminarily added to the porous polymer resin. 1. A method for producing an oxygen adsorbing/desorbing agent, which comprises introducing the complex into an axial ligand, dispersing and fixing the complex through ionic or covalent bonds, and then coordinating the complex with the axial ligand. 4. When producing an oxygen adsorbing/desorbing agent by dispersing and fixing a complex having oxygen adsorption ability in a porous polymer resin, a porous polymer in which an axial ligand that can coordinately bond the complex is dispersed and fixed. 70 to 130 in which the complex is dissolved in a polar solvent.
A method for producing an oxygen adsorbing/desorbing agent, which comprises immersing it in a complex solution at 0.degree. C. to form a coordinate bond between the complex and the axial ligand. 5. When producing an oxygen adsorbing/desorbing agent by dispersing and fixing a complex having oxygen adsorption ability in a porous polymer resin, an axis capable of coordinating the complex, which is dispersed and fixed in the porous polymer resin. 1. A method for producing an oxygen adsorbing/desorbing agent, which comprises binding the complex to a ligand and then removing the complex physically adsorbed to the porous polymer resin. 6. An axial ligand to which the complex can coordinately bond is introduced into a porous polymer resin by ionic bonding or covalent bonding and dispersed and fixed therein, and then the porous polymer in which the axial ligand is dispersed and fixed is prepared. The resin is immersed in a complex solution in which a complex having oxygen adsorption ability is dissolved in a polar solvent, and the complex solution is heated at 70 to 130°C.
The complex and the axial ligand are coordinately bonded by heating the porous polymer resin to a temperature of 1. A method for producing an oxygen adsorbing/desorbing agent, the method comprising: removing a complex containing an oxygen adsorbing/desorbing agent.