JPS6017363B2 - Method for producing polymer complex having gas adsorption/desorption ability - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polymeric body having a gas adsorption/desorption chamber.

Conventionally, there have been many reports on methods for manufacturing polymeric metal keys having gas adsorption/desorption capabilities.

For example, a polymeric metal rust body is produced by directly imitating a low-molecular metal rust body ligand with a polymeric ligand through a ligand substitution reaction in a solution, and the central metal is This is a method in which the ligand is reduced to a low valence state using a reducing agent before or at the same time as the ligand substitution reaction. However, the polymeric metal collar body obtained by the conventional method has several problems as described below. In a '1' solution, especially in an aqueous solution, the gas adsorption/desorption rate is relatively fast, but the central metal is easily oxidized and deteriorated, resulting in poor usability.

'21 Although the stability is improved in the form of solid powder or film, the rate of gas adsorption and desorption is not fast.

[31] Since a reduction operation of the central metal ion is required, impurities such as reducing agent fragments are likely to be mixed in, resulting in poor stability.

'41 has problems in solubility and stability, making it difficult to prepare it in the form of a film.

The present invention was made against the background of the above circumstances, and an object of the present invention is to provide a method for producing a polymer collar body that has a gas adsorption/desorption chamber and can be easily prepared in the form of a film. .

The method for producing a polymeric rust body having gas adsorption/desorption ability according to the present invention is characterized in that a polymer compound having a coordinating group has iron or cobalt in a high valence state as a central metal in the coordinating group, and voluphyrin , phthalocyanine or bis(
Salicylaldehyde) is produced by irradiating a vinyl compound and a high-molecular metal body coordinated with a low-molecular metal body having an ethylenediimine skeleton as a ligand with radiation in the absence of oxygen. It is characterized by reacting and reducing the metal to a low valence state.

That is, in the present invention, a polymer metal body (hereinafter referred to as reactant 1) is reacted with a pinyl compound under radiation irradiation.

This high-molecular metal body is produced by reacting a high-molecular compound having (a large number of) coordinating groups, that is, a high-molecular ligand, and a low-molecular metal body through a ligand substitution reaction in a solvent that dissolves both. obtained by. In this case, the molar ratio of the coordination group unit of the polymeric ligand to the low-molecular weight metal body is generally from 1:1 to 10,000:1, preferably from 100:1 to 1,000:1. Examples of polymeric ligands include primary amino groups, secondary amino groups, tertiary amino groups, nitrogen atom ring groups,
Any polymer compound can be used as long as it contains a large number of groups with coordinating ability such as Schiff's base, carboxyl group, and alcoholic hydroxyl group. However, among them, those particularly suitable for the purpose of reversibly adsorbing and desorbing gas are homopolymers or copolymers of nitrogen-containing vinyl monopolymers such as vinylpyridine, vinylimidazole, or derivatives thereof. , polyamino acids having many amino groups in their side chains, etc. The low-molecular metal key body used in this invention is
It has iron or cobalt, which has a high affinity with gas, as a central metal in a high valence state. This type of low-molecular-weight metal enantiomer can be used, as is well known in the art, to provide two or four chelating ligands to the salts of the transition metals, such as porphyrins, phthalocyanines, bis(salicylaldehydes), etc. It can be easily obtained by reacting ethylenedimine or the like. Note that as this chelate ligand, one having a coordinating group in the side chain can also be used.
The reaction between the reactant 1 and the vinyl compound is carried out in a solution in the absence of oxygen and under irradiation with radiation such as Y-rays and electron beams.

In practice, this reaction is carried out by degassing the reaction solution, sealing the tube, and irradiating it with radiation at room temperature. The irradiation dose is
From the viewpoint of the irradiation effect and the fact that the fin body is not destroyed,
1 and 5 megarads are appropriate. Any soluble vinyl compound can be used in this reaction. Typical examples include acrylic ester, acrylic amide, styrene, vinylpyrrolidone, and derivatives thereof. The concentration of this pinyl compound in the reaction solution is 10 to 2% by weight.
is preferred. The reaction time is about 3 to 5 hours.
In addition, the concentration of reactant 1 (unit unit) is 10-2 to 10
-4 mol/1 is preferred. Through the above radiation irradiation reaction, the pinyl compound polymerizes and takes in reactant 1 and reacts with reactant 1, thus forming a strong polymer in which the collar bodies are uniformly dispersed while retaining a desired proportion of the solvent. Obtained in the form of a film or sheet.

In these reactions, the central metal of the collar body receives free electrons ejected from solvent molecules by radiation irradiation, thereby reducing the central metal. Therefore, the reduction operation using a reducing agent, which is required in the conventional method, is not necessary, and as a result, a pure polymer body can be obtained. Note that the progress of these fin-forming reactions and reduction reactions can be accurately grasped by tracking changes over time in the visible spectra of the reaction solution and products. The product obtained in the above manner is purified by a very simple method, for example, by placing it in a solvent similar to that of the reaction solution under an inert atmosphere such as nitrogen to remove unreacted substances. be able to.

The polymer polymer obtained by the method of this invention is a gas (
When brought into contact with 02, C○, CQ, N○x), the ligand in the mari coordination site imitates a gas molecule, and the gas molecule adsorbs and binds as one of the axial ligands, creating a stable gas key. When a key body is formed and placed in an inert atmosphere, such as a nitrogen atmosphere or a vacuum, the adsorbed gas is released and the original key body structure is restored.

(Such phenomena can be detected by visible spectrum measurements, transmitted gas analysis, etc.) Furthermore, since the polymer mirror obtained by this invention contains a solvent in any proportion as described above, If it is used as is, it will absorb gas at a very high speed in the same way as a solution system, even though it is in a solid state, and there are many gas absorption groups. Furthermore, since the central active metal of this polymeric body is firmly fixed within the polymer region, the gaseous body can exist stably for a very long time, and the central active metal can be irreversibly oxidized. It can be used repeatedly as it also greatly reduces the loss of accommodation caused by this. Utilizing the properties described above, the polymer obtained by this invention can be used as an immobilized catalyst that captures specific gases from the air, as a gas carrier that can easily release gas, as well as as a photoconductive polymer and a photosensitive material. , can be used as a paramagnetic material. In addition to opening up a wide range of uses as an oxygen carrier, it is also expected to be used as an important material for artificial red blood cells. Alternatively, the solvent may be removed and used as it is or in the form of particles. The present invention will be described below with reference to Examples.

Example 1 Chlorohemin represented by the formula is dissolved in a 3:2 mixed solvent of NaHC03-N, C03 and methanol ([chlorohemin] = 0.1mM), and a polymer is added to this. 1-vinyl-2-methylimidazole/ as a ligand
1-Pinylpyrrolidone copolymer (molecular weight 60,000, 1-vinylpyrrolidone unit content 58%, hereinafter referred to as PMIP) 0.06
I often worshiped flies in the evening.

To this solution was added 1 part of hydroxyethyl methacrylate as a vinyl compound. This reaction solution was irradiated with y-rays from CO under a nitrogen atmosphere at room temperature for 4 hours at a dose rate of 5×1 pyrad/hour (irradiation dose: 2 megarads). In this way, a reddish-brown transparent film with a thickness of two legs was obtained. This was washed with the same solvent in a nitrogen atmosphere. This film has a central metal Fe (m) of F
It has a reduced heme structure that is converted to e(0), and the reaction process was followed by visible absorption spectrum measurement, and the results shown in FIG. 1 were obtained. As can be seen from this figure, as the reaction progresses, the absorption maximum characteristic of the oxidized heme present in 39-m, 56-m, and 59-tsumugi gradually decreases, and the absorption maximum gradually shifts to the longer wavelength side. , 424mm and 5
At 47 mm, an absorption maximum peculiar to reduced heme appeared. When oxygen was passed through the membrane and the visible absorption spectrum was measured after saturation, new absorption bands with maximum absorption at 41 mm, 52 mm, and 561 mm were observed.

When nitrogen gas was blown into this, the absorption bands with absorption maxima at 41mm, 52mm, and 561mm returned to the original absorption bands with absorption maxima at 424mm and 7mm. From this, it was found that the new absorption band was attributed to an oxygen ring body in which molecular oxygen was bonded to the heme marker coordination site. In addition, when CO and NO were injected into the membranes having the reduced heme mirror structure, 41.
Absorption bands with absorption maxima at 531 mm and 55 mm, and absorption bands with absorption maxima at 41 mm, 527 mm, and 55 mm, respectively, returned to their original absorption bands when replaced with nitrogen gas.

Note that the above operations could be repeated. Example 2 A desired polymer having a reduced heme structure was obtained by reacting in the same manner as in Example 1 except that vinylpyrrolidone was used instead of hydroxyethyl methacrylate.

It was confirmed by visible absorption spectrum measurement that when Q, CO, or NO was blown into this, these were adsorbed, and when this was left under an inert gas, the adsorbed gas was released.
The results are shown in Table 1 below together with the results of Example 1. Table 1 (Visible, maximum absorption wavelength) Styrene/4-vinylpyridine copolymer (molecular weight 10,000, 4-vinylpyridine unit quantity 23%) 0.05
After adding 100% of styrene and 10% of styrene and stirring well, the mixture was irradiated with 3 megarads of y-rays from 60 CO at room temperature under a nitrogen atmosphere.

In this way, a clear transparent desired polymer film was obtained. After washing this with toluene under a nitrogen atmosphere and blowing oxygen into it, the color gradually changed to deep purple. When nitrogen gas was blown into the dark purple film or it was heated, it returned to its original light color. When this change was measured by visible absorption spectrum, the spectrum shown in FIG. 2 was obtained. That is, initially the absorption maximum was at 357 mm and 41 m, and the absorption band had an ephemeris at 50 M sail, but when oxygen was injected, the absorption maximum was at 357 mm and 41 m.
The absorbance at 56°C gradually decreased, and a new absorption band appeared with an absorption maximum at 56°C.

[Brief explanation of the drawing]

Fig. 1 shows a visible absorption spectrum diagram during the reaction process of one example of a polymer chain body obtained by this invention, and Fig. 2 shows a visible absorption spectrum diagram accompanying oxygen adsorption/desorption of another polymer chain body obtained by this invention. Absorption spectrum diagram. 1. Figure 2

Claims (1)

[Scope of Claims] 1. A polymer compound having a coordinating group, which has iron or cobalt in a high valence state as a central metal in the coordinating group, and which has porphyrin, phthalocyanine, or bis(salicylaldehyde)ethylenediimine. A polymer metal complex formed by coordination of a low-molecular metal complex having a skeleton as a ligand is reacted with a vinyl compound in a solution state by irradiation with radiation in the absence of oxygen, and the metal is 1. A method for producing a polymer complex having gas adsorption/desorption ability, which is characterized by reduction to a low valence state. 2. The production method according to claim 1, wherein the polymer compound is a single or copolymer of a nitrogen-containing vinyl monomer or a polyamino acid. 3. The manufacturing method according to claim 2, wherein the nitrogen-containing vinyl monomer is vinylpyridine or vinylimidazole. 4. The manufacturing method according to any one of claims 1 to 3, wherein the vinyl compound is an acrylic ester, an acrylic amide, styrene, or vinylpyrrolidone. 5. The production method according to any one of claims 1 to 4, wherein the vinyl compound is present in a proportion of 10 to 20% by weight of the entire reaction system. 6. The manufacturing method according to any one of claims 1 to 5, wherein the radiation is a gamma ray or an electron beam. 7. The manufacturing method according to any one of claims 1 to 6, wherein the radiation dose is 1 to 5 megarads.