KR102130080B1 - Polymeric compound, oxygen permeable membrane, Electrochemical device - Google Patents

Abstract

A polyfunctional acrylate-based compound and a metal porphyrin derivative include a backbone cross-linked by binding to each other, and the metal porphyrin derivative is a polymer compound coordinated by a basic axis ligand at a fifth position of the metal, using the polymer compound Disclosed is an electrochemical device comprising an oxygen permeable membrane and a partition wall made of the oxygen permeable membrane. A polymer compound having improved oxygen selective permeability and an oxygen permeable membrane are provided, and an electrochemical device having excellent performance is provided.

Description

Polymer compounds, oxygen permeable membranes, and electrochemical devices

A polymer compound capable of selectively occluding or releasing oxygen, an oxygen permeable membrane using the polymer compound, and an electrochemical device using the oxygen permeable membrane.

Recently, as a secondary battery capable of charging and discharging, an electrochemical device using oxygen, such as a lithium air battery, as a positive electrode active material has attracted attention. In such an electrochemical device, oxygen is supplied from the outside of the device (air or external oxygen supply device) during charging and discharging, and this oxygen is used for the oxidation-reduction reaction in the electrode during charging and discharging. Therefore, it has become important for an electrochemical device using oxygen, such as a lithium air battery, for an oxidation-reduction reaction to quickly and efficiently collect oxygen in a certain way from the viewpoint of an increase in electric capacity and the like. In particular, it is desired to efficiently collect oxygen from air containing other components such as nitrogen. To this end, it is preferable to arrange a member capable of selectively binding (occluding, releasing) oxygen molecules to the inlet of oxygen to the anode (air electrode) of the electrochemical device.

As such a substance capable of selectively binding oxygen, for example, a cobalt porphyrin derivative in which cobalt is coordinated at the center of a porphyrin molecule is known. The cobalt porphyrin derivative has the same shape as hemoglobin, and is capable of selectively and reversibly binding oxygen molecules with one permeation of air. In the polymer membrane in which this cobalt porphyrin derivative is blown inside as an oxygen carrier, oxygen is selectively blown into the membrane and transported quickly. Therefore, since the membrane containing the cobalt porphyrin derivative is capable of selectively permeating oxygen, industrial applicability as an oxygen selective permeation membrane or oxygen enrichment membrane has been studied.

However, since the cobalt porphyrin derivative itself is a rigid molecule, it lacks flexibility, and conventionally, it emphasizes processability and maintains a self-supporting film. Therefore, the proportion of the polymer backbone other than the porphyrin derivative or the polymer material to be mixed must be increased. . Therefore, it is difficult to sufficiently express the function of selectively absorbing and releasing oxygen possessed by the cobalt porphyrin derivative, and further, the oxygen permeation function of the membrane using the cobalt porphyrin derivative. In addition, the film containing the cobalt porphyrin derivative as a main material has a problem that the selective permeability of oxygen is low in that the differential pressure associated with the membrane before and after the membrane is equal to or greater than the partial pressure of oxygen in the air.

Therefore, there is still a need for a polymer compound having improved oxygen selective permeability, an oxygen permeable membrane using the polymer compound, and an electrochemical device using the oxygen permeable membrane.

One aspect of the present invention is to improve an oxygen selective permeability of a metal porphyrin derivative by using a high molecular compound, an oxygen permeable membrane using the polymer compound, and the oxygen permeable membrane by improving the oxygen selective permeability of the metal porphyrin derivative even at a pressure difference of about the partial pressure of oxygen in the air It is to provide an electrochemical device having excellent performance.

According to one aspect,

A polyfunctional acrylate-based compound and a metal porphyrin derivative are bonded to each other to include a crosslinked backbone,

The metal porphyrin derivative is provided with a polymer compound coordinated by a basic axis ligand at the fifth position of the metal.

In the metal porphyrin derivative, an oxygen molecule may be coordinated to a sixth position located on the opposite side of the metal.

The basic axis ligand may include a nitrogen-containing organic ligand.

The metal porphyrin derivative may be a complex in which a metal is assigned to a tetraphenylporphyrin derivative represented by Formula 1 below:

<Formula 1>

In Chemical Formula 1,

R1, R2, R3 and R4 are each independently an amino group, acetoacetate group, acetoacetamide group, cyanoacetate group, cyanoacetamide group, hydrogen, halogen group, It may be a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C6-C10 aryl group, or a combination thereof. ,

However, at least one of R1, R2, R3 and R4 is selected from an amino group, acetoacetate group, acetoacetamide group, cyanoacetate group, and cyanoacetamide group. Group.

The polyfunctional acrylate-based compound and the metal porphyrin derivative may include a backbone cross-linked by binding to each other by a Michael-type addition reaction.

The content of the metal porphyrin derivative per unit content of the polymer compound may be 30% by weight or more.

According to another aspect,

An oxygen permeable membrane using the polymer compound is provided.

In the oxygen permeable membrane, the oxygen permeability coefficient with respect to the nitrogen permeability coefficient may be 8 times or more at 1 cmHg or more and 2 times or more at 50 cmHg or more before and after the membrane.

According to another aspect,

Anode using oxygen as a cathode active material,

A negative electrode which is a negative electrode active material that can occlude and release lithium ions,

An electrolyte disposed between the positive electrode and the negative electrode, and

It has a partition wall made of the above-described oxygen permeable membrane,

An electrochemical device for supplying oxygen to the anode via the partition wall is provided.

It is possible to improve the oxygen-selective permeability of a polymer compound containing a metal porphyrin derivative, even at a pressure difference above the partial pressure of oxygen in the air, to provide an oxygen-permeable membrane using the polymer compound, and also to have excellent battery performance by using the oxygen-permeable membrane. An electrochemical device can be provided.

1A is an explanatory diagram conceptually showing a structure of a polymer compound according to an embodiment.
1B is an explanatory diagram conceptually showing a structure of a polymer compound according to an embodiment.
2 is a schematic diagram showing a lithium air battery according to an embodiment.
3 is a spectrum showing IR measurement results before and after curing of the oxygen-permeable membrane of Example 1.
4A is a characteristic diagram showing the relationship between the differential pressure of oxygen and nitrogen (p ₁ -p ₂ : horizontal axis) and the transmission coefficient of oxygen and nitrogen (P: vertical axis) in the oxygen permeable membrane of Comparative Example 1;
4B is a characteristic diagram showing the relationship between the differential pressure (p ₁ -p ₂ : horizontal axis) of oxygen and nitrogen and the oxygen transmission coefficient (P: vertical axis) in the oxygen-permeable membrane of Example 1. FIG.

Hereinafter, a polymer compound, an oxygen permeable membrane, and an electrochemical device according to an embodiment will be described in detail. This is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of claims to be described later.

[One. Polymer compound]

In one aspect, a polyfunctional acrylate-based compound and a metal porphyrin derivative include a backbone cross-linked by binding to each other, and the metal porphyrin derivative provides a polymer compound coordinated by a basic axis ligand at a fifth position of the metal do. In the metal porphyrin derivative, an oxygen molecule may be coordinated to a sixth position located on the opposite side of the metal. The basic axis ligand may include a nitrogen-containing organic ligand. The basic axis ligand will be described later.

The polymer compound includes a polyfunctional acrylate-based compound and a metal porphyrin derivative that are bonded to each other and crosslinked to form a large amount of the metal porphyrin derivative in the polymer compound, including a crosslinked backbone. Without it, it can maintain the selective permeation function of oxygen.

In addition, a basic axial ligand binds to the fifth position of the central metal of the metal porphyrin derivative, so that coordination of oxygen molecules at the sixth position of the central metal is facilitated, and thus a polymer compound containing a metal porphyrin derivative even at an oxygen partial pressure level higher in the air. Oxygen selective permeability of can be improved.

[1.1. Structure of polymer compound]

The structure of the polymer compound will be described with reference to FIG. 1. 1A is an explanatory diagram conceptually showing a structure of a polymer compound according to an embodiment. 1B is an explanatory diagram conceptually showing a structure of a polymer compound according to an embodiment. On the other hand, hereinafter, unless otherwise specified, the acrylate-based compound means "(meth)acrylate-based compound."

The polymer compound may include a backbone in which the polyfunctional acrylate compound and the metal porphyrin derivative are cross-linked by binding to each other by a Michael-type addition reaction.

In detail, the metal porphyrin derivative contains at least one nucleophilic functional group, and a part or all of the nucleophilic functional group and the acrylic group included in the polyfunctional acrylate compound are crosslinked by binding to each other by Michael type addition reaction Backbone. Sites derived from the metal porphyrin derivative may be present in the main or side chain of the backbone.

The metal porphyrin derivative may be a metal porphyrin complex. For example, the metal porphyrin complex may be a cobalt porphyrin complex. That is, in the polymer compound, the cobalt porphyrin complex may be combined with a polyfunctional acrylate-based compound, and a backbone may be formed together with the acrylate compound. Sites derived from the cobalt porphyrin complex may be present in the main or side chain of the backbone. A basic axial ligand binds to the fifth position of cobalt of the cobalt porphyrin complex, thereby facilitating oxygen molecules to coordinate at the sixth position of cobalt, so that the differential pressures before and after the membrane are more than the partial pressure of oxygen in the air. Transport can be realized. As a result, it is possible to improve the electrochemical performance of an electrochemical device such as an air battery using air as a positive electrode active material.

The content of the metal porphyrin derivative per unit content of the polymer compound may be 30% by weight or more.

(Polyfunctional acrylate compound)

The polyfunctional acrylate-based compound has two or more acrylic groups, and may be a Michael acceptor in a Michael type addition reaction. However, in a monofunctional acrylate-based compound, a polymer skeleton cannot be formed together with a metal porphyrin derivative described later, for example, a cobalt porphyrin complex.

The polyfunctional acrylate-based compounds include, for example, reactive monomers such as neopentyl glycol diacrylate and dipropylene acrylic diacrylate, and reactive oligomers such as polyethylene glycol diacrylate, urethane acrylate, and epoxy acrylate. Reactive monomers such as difunctional acrylate, trimethyrolpropane triacrylate and pentaerythritol triacrylate, reactive monomers such as reactive oligomer, trifunctional acrylate such as pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate And acrylate or higher acrylates such as oligomers.

Among these, the polyfunctional acrylate-based compound may be a short-chain acrylate-based compound having 20 or more carbon atoms. As such a short-chain acrylate-based compound, it is preferable to use, for example, diacrylate represented by <Formula 2>, triacrylate represented by <Formula 3>, and tetraacrylate represented by <Formula 4> . By using such a short-chain acrylate-based compound, the content of a metal porphyrin derivative per molecule of a polymer compound, for example, a cobalt porphyrin complex, can be increased.

<Formula 2>

<Formula 3>

<Formula 4>

Meanwhile, as the polyfunctional acrylate-based compound, the aforementioned bifunctional acrylate or polyfunctional acrylate may be used alone, or two or more kinds may be used in combination. In addition, the above-mentioned bifunctional acrylate and polyfunctional acrylate may be synthesized by a known method, or a commercially available one may be used.

In addition, the polyfunctional acrylate-based compound may include an alkylene group substituted with halogen. The polyfunctional acrylate-based compound and a metal porphyrin derivative, for example, a polymer compound synthesized using a cobalt porphyrin complex, may have water repellency. The polyfunctional acrylate compound having an alkylene group substituted with halogen is not particularly limited, but may be, for example, diacrylate represented by <Formula 5>.

<Formula 5>

(Metal porphyrin derivative)

The metal porphyrin derivative may be a complex in which a metal is assigned to a tetraphenylporphyrin derivative represented by Formula 1 below:

<Formula 1>

In Chemical Formula 1,

R1, R2, R3 and R4 are each independently an amino group, acetoacetate group, acetoacetamide group, cyanoacetate group, cyanoacetamide group, hydrogen, halogen group, It may be a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C6-C10 aryl group, or a combination thereof. ,

However, at least one of R1, R2, R3 and R4 is selected from an amino group, acetoacetate group, acetoacetamide group, cyanoacetate group, and cyanoacetamide group. Group.

The metal porphyrin derivative may be, for example, a cobalt porphyrin complex. Specifically, the metal porphyrin derivative may be a complex in which cobalt is assigned as a metal to the tetraphenylporphyrin derivative represented by Chemical Formula 1.

Here, in Formula 1, R1, R2, R3 and R4 are nucleophilic functional groups, that is, functional groups that can be Michael donor. "Michael donor" as used herein means a part (functional group) that can be a so-called Michael donor in a Michael-type addition reaction.

Examples of the nucleophilic functional group include a nitrogen atom having a non-covalent electron band, a functional group having an oxygen atom, and the like. More specifically, the above-described amino group, acetoacetate group, acetoacetamide group, and cyano It may be a noacetate (cyanoacetate) group, or a cyanoacetamide group. Among these, it is preferable to use an amino group or an acetoacetate group, but in order to coordinate porphyrin cobalt having an amino group, solubility in a cast solution may be lowered and film formation may be difficult. Therefore, when using the polymer compound for use as an oxygen permeable membrane, it is preferable to use an acetoacetate group rather than an amino group.

Further, in Formula 1, R1, R2, R3 and R4 are not particularly limited as substituents (residues) other than the nucleophilic functional group, but have a small molecular weight that does not reduce the content of the cobalt porphyrin complex in the polymer compound. Substituents of can be used. Examples of such residues include hydrogen, halogen groups, substituted or unsubstituted C1-C10 alkyl groups, substituted or unsubstituted C2-C10 alkenyl groups, substituted or unsubstituted C2-C10 alkynyl groups, substituted or unsubstituted C6-C10 Can be an aryl group of

Substitution in the "substitution" is a halogen atom, a C1-C10 alkyl group substituted with a halogen atom (for example, CCF ₃ , CHCF ₂ , CH ₂ F, CCl _3, etc.), hydroxy group, nitro group, cyano group, amino group, amidino Group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, or alkyl group of C1-C10, alkenyl group of C2-C10, alkynyl group of C2-C10, heteroalkyl group of C1-C10, It means substituted with C6-C10 aryl group, C6-C10 arylalkyl group, C6-C10 heteroaryl group, or C6-C10 heteroarylalkyl group.

Here, when the above-mentioned polyfunctional acrylate-based compound is only a bifunctional acrylate, there is only one nucleophilic functional group of the tetraphenylporphyrin derivative, that is, only one of R1 to R4 in <Formula 1> If it is a nucleophilic functional group, a cobalt porphyrin complex and a polyfunctional acrylate-based compound cannot form a crosslinkable polymer skeleton. Therefore, when the polyfunctional acrylate-based compound is only bifunctional acrylate, it is necessary for the tetraphenylporphyrin derivative to have at least two nucleophilic functional groups.

On the other hand, when the aforementioned polyfunctional acrylate-based compound contains at least one or more bifunctional or higher polyfunctional acrylates, even if there is only one nucleophilic functional group of the tetraphenyl porphyrin derivative, the cobalt porphyrin complex and the polyfunctional acrylic The rate can form a crosslinkable polymer backbone. Accordingly, when the polyfunctional acrylate-based compound contains at least one or more bifunctional or higher polyfunctional acrylates, the tetraphenylsulpyrin derivative may have at least one nucleophilic functional group.

(Basic Axis Coordinator)

By a basic axial ligand coordinated to the fifth position of the cobalt which is the central metal in the metal porphyrin derivative, for example, the cobalt porphyrin complex, the sixth position opposite the fifth position and cobalt in the axial direction of the cobalt porphyrin complex. Oxygen molecules can be preferentially coordinated to the coordination site. Thereby, even if the differential pressure related to the front and rear of the membrane is equal to or greater than the partial pressure of oxygen in the air, oxygen-promoted transport by the cobalt porphyrin complex can be realized. This can significantly improve the oxygen selective permeability of the cobalt porphyrin complex.

As the basic axis ligand, a molecule having a functional group having a high electron donor is preferred, such as having a non-covalent electron band. Some of these basic axis ligands have amino groups, phosphino groups, carboxy groups, thiol groups, and the like.

The basic axis ligand may include a nitrogen-containing organic ligand. As the nitrogen-containing organic ligand, amines (methylamine, trimethylamine, etheramine, pyridine, hexamethylenediamine, morpholine, aniline, etc.), imines (ethyleneimine, sif base, etc.), imidazoles (methylimidazole , Benzyl imidazole, trimethyl imidazole, and the like).

In addition, other organic ligands include triphenylphosphine, acetyl acetate, and ethers. The following 1-benzyl-1H-imidazole (BIm) is exemplified as the basic axis ligand.

The basic axial ligand has a high basicity, that is, a high electron donor increases the oxygen affinity of a metal porphyrin derivative, for example, a cobalt porphyrin complex. This can be interpreted because, when the electron donation is strong, the electron transfer from the Co to the π* orbit of the oxygen molecule is facilitated, thereby facilitating the formation of a bond between Co-O ₂ . It can be considered that the electron state of Co-O ₂ rather than various interpretations actually asserts the polarization state of Co(III) ⁺ -O ₂ -rather than Co(II)-O ₂ .

When the distance between Co-N is increased due to the steric hindrance of the cobalt porphyrin complex and the distortion of the molecule, the electronic effect of the basic axis ligand is affected, and the coordination ability of the basic axis ligand to the cobalt porphyrin complex tends to deteriorate. . That is, due to steric hindrance and distortion, the basic axis ligand becomes difficult to access to the cobalt porphyrin complex, and the electronic bond is weakened (the distance between Co-N is widened), thereby deteriorating the coordination ability.

If the UV-vis spectrum of the cobalt porphyrin complex is measured, the soret and Q bands are maximized. If a 5-axis equivalent of a basic axis ligand (imidazole) is added to the cobalt porphyrin complex, it can be confirmed that the peak of the Q band shifts a long wavelength, and the basic axis ligand coordinates to the cobalt porphyrin complex. On the other hand, even when a basic axial ligand was present in a cobalt porphyrin complex that is very excessive (100 equivalents), nothing else was confirmed in the spectrum, so a basic axial ligand was added in 5 equivalents to the cobalt porphyrin complex to make it nearly 100%, and the basic axial ligand was It may be thought that the ligand is coordinating for the cobalt porphyrin complex. In addition, after coordinating the basic axial ligand to the cobalt porphyrin complex, if exposed to oxygen, it can be confirmed that the soret band and the Q band shifted with a long wavelength shift. Therefore, the basic axis ligand coordinates the cobalt porphyrin complex at the fifth position of the cobalt, and the oxygen molecule at the sixth position of the cobalt.

(Polymer compound)

A polyfunctional acrylate-based compound and a metal porphyrin derivative, for example, a cobalt porphyrin complex, can be subjected to Michael type addition reaction. In this reaction, a part or all of the nucleophilic functional group (for example, amino group or acetoacetate group) of the cobalt porphyrin complex is added to the acrylic group of the acrylate compound. The structure of the polymer compound having a backbone obtained by such an addition reaction will be described with reference to Figs. 1A and 1B. On the other hand, what is indicated by "Por" in Figs. 1A and 1B indicates that porphyrin is present at the position described as "Por". That is, a site derived from a cobalt porphyrin complex is present in a portion described as "Por".

<Example 1>

As a first example of the structure that the polymer compound may have, as shown in Fig. 1A, a cobalt porphyrin complex is a structure present in the main chain of a backbone obtained by Michael-type addition reaction of a polyfunctional acrylate-based compound and a cobalt porphyrin complex. In this case, the polyfunctional acrylate-based compound and the cobalt porphyrin complex can be combined with each other through a medium. That is, the same kind as the polyfunctional acrylate-based compound (cobalt porphyrin complex) can be combined via the cobalt porphyrin complex (polyfunctional acrylate compound).

Such a structure can be obtained, for example, by Michael addition of a tetrasubstituted cobalt porphyrin complex having four nucleophilic functional groups to a bifunctional acrylate or a polyfunctional acrylate compound of trifunctional or tetrafunctional or higher acrylate. have. However, when the bifunctional acrylate compound and the tetrasubstituted cobalt porphyrin complex are reacted, the crosslinking degree is low (the bonding point between the bifunctional acrylate compound and the cobalt porphyrin complex is small), and it is easy to dissolve in an organic solvent, making film formation difficult. There is a concern that the film strength may be weakened. On the other hand, when the tetrafunctional acrylate compound is reacted with the tetrasubstituted cobalt porphyrin complex, it may be insoluble or poorly soluble in the organic solvent. However, in this case, since there are too many crosslinking points (bonding point of the tetrafunctional acrylate compound and the cobalt porphyrin complex), the film tends to be brittle when formed. Therefore, it is more difficult to dissolve in an organic solvent and, in order to reduce the crosslinking point, it is more preferable to have a structure as in the second example described below.

<Example 2>

As a second example of the polymer compound, as shown in Fig. 1B, a cobalt porphyrin complex is a structure present in a side chain of a backbone obtained by Michael-type addition reaction of a polyfunctional acrylate-based compound and a cobalt porphyrin complex. In this case, a polyacrylate may be formed in the main chain by polymerizing the same kind of polyfunctional acrylate-based compound (copolymerization when two or more kinds of polyfunctional acrylate-based compounds are used), and side chains of the polyacrylate It is a structure in which a cobalt porphyrin complex is attached to a part.

Such a structure can be obtained, for example, by Michael-type addition of a monosubstituted cobalt porphyrin complex in which the tetrafunctional acrylate compound has only one nucleophilic functional group. In this case, the number of crosslinking points can be made compatible by balancing the properties in which it is difficult to dissolve in an organic solvent and the brittle properties of the film when formed.

<Molecular weight of polymer compound (polymerization degree)>

The molecular weight (or degree of polymerization) of the polymer compound is not particularly defined, and may be appropriately adjusted in response to the use of the polymer compound.

[1.2. Synthesis of polymer compounds]

Next, a method for synthesizing a polymer compound having the above-described configuration will be described.

The polymer compound can be obtained by adding a cobalt porphyrin complex having at least one nucleophilic functional group to a polyfunctional acrylic compound, that is, a bifunctional or polyfunctional acrylate compound, by Michael-type addition reaction, as described above. have. More specifically, when synthesizing the polymer compound, a polyfunctional acrylate that uses the Michael-type addition reaction and functions as a nucleophilic functional group (amino group, acetoacetate group, etc.) serving as a Michael donor, as a Michael acceptor. The cobalt porphyrin complex can be added to the polyfunctional acrylate-based compound by reacting with the acrylic group of the compound. Hereinafter, it demonstrates in more detail.

(Preparation of polyfunctional acrylate-based compounds)

First, a polyfunctional acrylate-based compound used for the synthesis of the polymer compound is prepared. These polyfunctional acrylate-based compounds may be synthesized by a known method, or commercially available ones may be used. As commercially available ones, for example, neopentyl glycol diacrylate (from Aldrich), pentaerythritol tetraacrylate (from Aldrich), 1,4-bis (acryloyloxy) butane (from TCI), 1, 10-bis (acryloyloxy) decane (manufactured by TCI), tetraethylene glycol diacrylate (manufactured by TCI), pentaerythritol triacrylate (manufactured by New China, Ltd.), bisphenol A type epoxy acrylate (Diecel Cytec), aliphatic urethane acrylate (Daicel Cytec), and the like.

(Synthesis of tetraphenylporphyrin derivatives)

Tetraphenylporphyrin may be synthesized by a known method, or a commercially available one may be used. As what is marketed, tetraphenylporphyrin (made by TCI, Wako Chemical, Sigma Aldrich, Strem Chemicals, etc.) can be mentioned, for example.

Next, nucleophilic functional groups such as amino groups and acetoacetate groups are introduced into the tetraphenylporphyrin. As the method for introducing the nucleophilic functional group, a known organic synthesis reaction may be used, but as an example, a method for introducing an amino group (mono- to tri-substituted) is shown below.

First, in the case of introducing an amino group, for example, as shown in the following <Formula 7> (Reaction Scheme 1), tetraphenylporphyrin and sodium nitrite are reacted in trifluoroacetic acid, and 1 to 3 nitro groups are reacted. The introduced tetraphenylsulpirin derivative is synthesized. Next, the introduced nitro group can be reduced using a reducing agent such as concentrated hydrochloric acid to synthesize a tetraphenylporphyrin derivative having 1 to 3 amino groups introduced therein.

<Formula 7>

(Reaction scheme 1)

Moreover, as a tetraphenyl sulfyrin derivative, you may use what is commercially available as well as synthetically. As such a commercial item, 5, 10, 15, 20-tetrakis(4-aminophenyl)-21H, 23H-porpine (made by TCI) etc. can be mentioned, for example.

(Cobalt coordination)

As a method for coordinating the cobalt to the tetraphenylporphyrin derivative synthesized as described above, a known method can be used and is not particularly limited, but, for example, a tetraphenylporphyrin derivative can be obtained from dimethylformamide (DMF) and chloroform. By dissolving in a mixed solvent and reacting with cobalt chloride hexahydrate in the presence of lutidine, a cobalt porphyrin complex to which cobalt is assigned to a tetraphenylporphyrin derivative can be synthesized.

(Michael type addition reaction)

Next, a polymer compound can be synthesized by dissolving a cobalt porphyrin complex synthesized as described above and an acrylate compound in a solvent, adding a catalyst, and performing a Michael-type addition reaction.

As the solvent usable at this time, for example, acetone, chloroform, benzene, toluene, tetrahydrofuran, ethanol, 2,2,2-trifluoroethanol, t-butylacetoacetate, etc., are used cobalt porphyrin complexes and acrylics The solubility of the rate compound can be appropriately selected.

In addition, as a usable catalyst, a catalyst that can be commonly used for the Michael-type addition reaction can be appropriately selected and used. For example, as an amine catalyst, diazabicycloundecene (DBU), tetramethylethylenediamine, tetra As a base catalyst, such as methylalkylenediamine and N-methyldicyclohexylamine, quaternary ammonium hydroxides such as sodium methoxide, sodium ethoxide, potassium tertiary butoxide, sodium hydroxide and tetramethylammonium hydroxide , Metal sodium, butyl lithium and the like, and, as the organometallic catalyst, ruthenium cyclooctadiene cyclooctatriene, iron acetyl acetate, nickel acetyl acetate, and the like can be exemplified. Among these, it is more preferable to use a catalyst that does not contain metal.

(Coordination of basic axis ligands)

Before the Michael type addition reaction of the cobalt porphyrin complex with the polyfunctional acrylate-based compound, the cobalt porphyrin complex is dissolved in a solvent, and then, to the solution, a basic catalytic ligand such as methylimidazole or benzylimidazole is added, , It is possible to react a cobalt porphyrin complex with a basic axis coordination compound.

[1.3. Effect of polymer compound]

According to the polymer compound described above, the crosslinking point between the cobalt porphyrin complex and the polyfunctional acrylate compound, that is, the binding point between the nucleophilic functional group of the cobalt porphyrin complex and the acrylic group of the polyfunctional acrylate-based compound can be increased more than before. . Therefore, according to the present invention, it is possible to obtain a polymer having a higher porphyrin content (the ratio of the content of the cobalt porphyrin complex per unit content of the polymer compound) than in the prior art. For example, the content of the metal porphyrin derivative per unit content of the polymer compound may be 30% by weight or more.

In particular, by using a short-chain acrylate as a polyfunctional acrylate-based compound, the porphyrin content can be significantly increased compared to a compound containing a conventional cobalt porphyrin complex.

In addition, by introducing a fluorine group into the alkylene chain of the polyfunctional acrylate-based compound, the water repellency of the polymer compound containing the cobalt porphyrin complex can be improved.

Moreover, by binding the basic axial ligand to the fifth position of the cobalt porphyrin complex, the oxygen molecule can be preferentially coordinated to the fifth position in the axial direction of the cobalt porphyrin complex and to the sixth position on the opposite side of the cobalt. have. Thus, accelerated transport of oxygen can be realized. This can significantly improve the oxygen selective permeability of the cobalt porphyrin complex even under a pressure equal to or greater than the partial pressure of oxygen in the atmosphere (about 15 cmHg). This effect makes it possible to selectively supply oxygen to the electrochemical device even when the electrochemical device operating by consuming oxygen needs more current. At the same time, it is possible to increase the oxygen concentration, and it is possible to reduce the overvoltage of the oxygen reduction reaction.

[2. Oxygen permeable membrane, oxygen permeable material]

Next, an oxygen permeable membrane and an oxygen permeable material using the above-described polymer compound will be described. Since the oxygen-permeable membrane using the above-described polymer compound is a self-supporting membrane rich in flexibility that can be obtained by forming the above-described polymer compound, it can be used for various purposes such as partition walls of an electrochemical device. Here, the polymer compound has a high porphyrin content, that is, a content of a cobalt porphyrin complex, but has a function of selectively binding (absorbing and releasing) oxygen molecules to the cobalt porphyrin complex. For this reason, the oxygen permeable membrane formed by forming a polymer compound has a high oxygen permeability, and can selectively permeate a large amount of oxygen.

Moreover, since a polymer compound excellent in water repellency can be obtained by using a polyfunctional acrylate-based compound having a fluorine group introduced into an alkylene chain, the oxygen-permeable membrane formed by forming the polymer compound has high oxygen permeability and water repellency. It can be provided in combination, and it becomes possible to realize higher and higher functionalization of the oxygen permeable membrane. In this case, since the unit of the polyfunctional acrylate-based compound having a fluorine group is excellent in oxygen permeability, not only the oxygen diffusion in the film becomes rapid, but also the water repellent effect of the film itself can be obtained, so that the surface of the oxygen permeable film is obtained. It can be prevented that the intake of oxygen into the film can be inhibited by the attached water droplets or the like. Therefore, it is possible to stably supply oxygen to the electrochemical device by providing the oxygen permeable membrane at an intake port of oxygen in, for example, an electrochemical device.

In addition, the oxygen permeable membrane may be a composite oxygen permeable membrane formed on the porous substrate or in the pores of the porous substrate, that is, the oxygen permeable material. As described above, by using the oxygen permeable membrane, the water repellency and durability of the oxygen permeable membrane made of the oxygen permeable membrane and the porous substrate can be improved by being supported on the porous substrate. It can stably maintain the oxygen permeability. Therefore, by providing this oxygen permeable material at an intake port of oxygen in, for example, an electrochemical device, it becomes possible to supply oxygen stably and long-term by the electrochemical device.

Since the content (existence ratio) of the cobalt porphyrin complex in the oxygen permeable membrane is high and the basic axial ligand is axially coordinated to the cobalt porphyrin complex, this oxygen permeable membrane may be formed on the porous substrate, or even within the pores of the porous substrate. Compared to the conventional cobalt porphyrin complex-containing membrane, it exhibits good oxygen permeability.

In the case of preparing an oxygen permeable material, an acetate-substituted cobalt porphyrin complex and a polyfunctional acrylate-based compound solution in which a basic axis ligand is bonded to a porous substrate is applied by a bar coater method or the like, and then a Michael type addition reaction at room temperature The polymer can be formed by executing. A spray coater method, a slit coater method, a slit and spin coater method, a spin coater method, an inkjet method other than the bar coater method may be used. As the porous support, for example, a microporous polymer sheet (polypropylene, polyethylene, or formerly, CellGuard 2400 (trade name: Toho Corporation)) can be selected.

Before the oxygen permeable membrane is coated on the porous substrate, a gas permeable polymer membrane may be applied in advance. The gas-permeable polymer film may be formed of poly(1-trimethylsilylpropene) represented by the following <Formula 8>. If a poly(1-trimethylsilylpropene) gas permeable membrane is formed between the oxygen permeable membrane and the porous substrate, the gas permeable membrane can increase the strength of the oxygen permeable membrane and/or oxygen permeable material without impairing the oxygen permeability. . The gas-permeable polymer may be synthesized by a known method, or a commercially available one such as poly(1-trimethylsilyl-1-propene) (manufactured by Tokyo Chemical Industry Co., Ltd.) may be used.

<Formula 8>

In the oxygen permeable membrane, the oxygen permeability coefficient with respect to the nitrogen permeability coefficient may be 8 times or more at 1 cmHg or more and 2 times or more at 50 cmHg or more before and after the membrane.

[3. Electrochemical device]

Next, an electrochemical device using the above-described oxygen permeable membrane or oxygen permeable material will be described in detail. The electrochemical device uses an oxidation-reduction reaction of oxygen. As such an electrochemical device, for example, a metal air cell and a fuel cell, etc., in the following description, the metal air cell will be described as an example.

The metal air battery uses oxygen as a positive electrode active material and metal as a negative electrode active material. It is a battery that can be charged and discharged. Since the positive electrode active material, oxygen, is obtained from air, it is not necessary to fill the positive electrode active material in the battery, so that the proportion of the negative electrode active material in the electric container can be increased, and thus, in theory, the capacity can be greater than that of the secondary battery using the solid positive electrode active material. have.

In a metal air battery, the reaction of the following formula (A) progresses at the time of charging, at the cathode. On the other hand, in the examples below, the case where lithium is used as the negative electrode active material is listed as an example.

The electrons generated in the formula (A) reach the anode via an external circuit. The lithium ions (Li ⁺ ) formed in the formula (A) move in the electrolyte disposed between the negative electrode and the positive electrode by electrical penetration from the negative electrode side to the positive electrode side.

In addition, during discharge, the reactions of the following (B) and (C) formulas proceed at the anode.

Lithium peroxide (Li ₂ O ₂ ) and lithium oxide (Li ₂ O) formed at the anode may accumulate at the anode, which is a cathode as a solid. During charging, the reverse reaction of the formula (A) and the reaction of the formulas (B) and (C) at the anode proceed, respectively, and metal (lithium) is regenerated at the cathode, so re-discharge is possible. do.

The electrochemical device includes a positive electrode using oxygen as a positive electrode active material, a negative electrode using a material capable of storing and releasing lithium ions as a negative electrode active material, an electrolyte disposed between the positive electrode and the negative electrode, and a partition wall made of the above-described oxygen permeable membrane. And, it is possible to supply oxygen to the anode through the partition wall.

2 is a schematic diagram showing a lithium air battery 100 according to an embodiment.

Referring to FIG. 2, the lithium air battery 100 has an anode 110, a cathode 120, and an electrolyte 130 disposed between the anode 110 and the cathode 120.

The positive electrode 110 includes a current collector 111 and a catalyst layer 112, and oxygen is used as a positive electrode active material. The current collector 111 is porous, and can also serve as a gas diffusion layer capable of diffusing air, and it is easy to increase the surface area so that a large amount of oxygen can be blown into the anode, and conductivity is improved. If it has, it will not be specifically limited. Examples include stainless steel, nickel, aluminum, iron, titanium, and carbon. The shape of the current collector 111 includes, for example, a foil, plate, mesh, grid, and the like, and more specifically, may be a mesh. The mesh shape is suitable because of its excellent current collection efficiency.

The catalyst layer 112 may use platinum, gold, silver, manganese oxide, iron oxide, etc., for example, electron acceptor donors having a porphyrin ring as a reducing catalyst and electron-accepting inhibitors such as fullerene derivatives It may include a molecule connected by an acceptor through an electrically conductive spacer. The donor may be, for example, a compound having a substituted or unsubstituted porphyrin ring, for example, a porphyrin-metal complex substituted with Mg or Ni. In this case, the substituent may be, for example, a C1-C10 alkyl group, a C1-C10 alkynyl group, or a C6-C10 aryl group. The acceptor may be, for example, a derivative having a fullerene skeleton such as C60, C70, C74, or C76, and the spacer may be, for example, a condensed nitrogen-containing heterocycle or a hydrocarbon ring. However, it is possible to use any catalyst that can be used as the catalyst layer of the positive electrode using oxygen as the positive electrode active material in addition to the catalyst.

The positive electrode 110 may suitably add a conductive material, a binder, a dispersant, and a thickener. As the conductive material, any electroconductive material can be used without limitation, without impairing the electrochemical performance of the electrochemical device of the present invention. Specifically, natural graphite, carbon black, ketjen black, carbon fiber, and the like can be listed. These conductive materials may be used alone or in combination. As the binder, any material that can bind the active material and the conductive material can be used without limitation. Specifically, fluorine-based resins such as polytetrafluoroethylene and polyvinylidene fluoride, thermoplastic resins such as polypropylene, and the like can be listed. The content of the binder is not particularly limited, and may be, for example, 30% by weight or less, and more specifically, 1 to 10% by weight.

The negative electrode 120 includes a current collector (not shown) and a negative electrode active material.

The current collector of the negative electrode is not particularly limited as long as it has conductivity. For example, copper, stainless steel, nickel, etc. are mentioned. Examples of the shape of the current collector of the negative electrode include a foil, a plate, a mesh, and a grid.

As the negative electrode active material, a material capable of absorbing and releasing lithium ions such as lithium, lithium oxide, and lithium alloy may be used without limitation. For example, lithium metal can be used.

The negative electrode 120 may appropriately add a conductive material, a binder, a dispersant, and a thickener. At this time, the conductive material, binder, dispersant, and thickener used may be the same type and content as the anode 110.

The positive electrode 110 and the negative electrode 120 may be mixed and dispersed in a suitable solvent to form a paste-like positive electrode material and a negative electrode material. In addition to the positive electrode active material and the negative electrode active material, a conductive material and a binder may be appropriately added to the positive electrode material and the negative electrode material. The resulting positive electrode material and negative electrode material can be applied to the surface of the current collector to form a negative electrode layer.

The electrolyte 130 may conduct metal ions (eg, lithium ions) of the negative electrode active material, and as long as it is capable of dissolving the oxygen adsorption/desorption material, an aqueous electrolyte, a non-aqueous electrolyte, or without particular limitation, Polymer gel electrolytes and the like can be used.

The electrolyte 130 may be, for example, a non-aqueous electrolyte.

Examples of the solvent for the non-aqueous electrolyte include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate and vinylene carbonate, chain carbonates such as diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate, gamma butyrolactone, and gamma. In addition to cyclic ester carbonates such as valerolactone, cyclic ethers such as tetrahydrofuran and 2-methyltetrahydrofuran, and chain ethers such as dimethoxyethane and ethylene glycol dimethyl ether, chloroethylene carbonate, fluoroethylene carbonate, 3- Known organic solvents such as methoxypropionitrile, trimethyl phosphate, triphenyl phosphate, sulfolane, and dimethyl sulfoxide can be used.

Also, N, N-diethyl-N-ethyl-N-(2-methoxyethyl)ammonium bis(trifluorosulfonyl)imide, N-methyl-N-propylpiperidium bis(trifluorosulfonyl) )Imide, 1-methyl-3-propylimidazolium miss (trifluorosulfonyl)imide, ionic liquid such as 1-ethyl-3-butylimidazolium tetrafluoroborate, etc. may be used. . These solvents may be used alone or in combination of two or more.

The electrolyte may further include a supporting salt. The supporting salt is dissolved in the solvent, and may serve as a source of lithium ions in the battery. As the support salt, for example, hexafluorophosphenone salt (LiPF ₆ ), perchlorate salt (LiClO ₄ ), tetrafluoroborate salt (LiBF ₄ ), pentafluoroarsine salt (LiAsF ₅ ), bis (trifluor Romethanesulfonyl)imide salt (Li(CF ₃ SO ₂ ) ₂ N), bis(pentafluoroethanesulfonyl)imide salt (LiN(C ₂ F ₅ SO ₂ ) ₂ ), trifluoromethanesulfonate ( Li(CF ₃ SO ₃ )), nonafluorobutanesulfonic acid salt (Li(C ₄ F ₉ SO ₃ )), and the like. The support salts may be used alone or in combination of two or more.

However, from the viewpoint that the oxygen molecule can be coordinated to the oxygen molecule at the sixth position of the tetraphenylporphyrin complex, it is preferable to select an appropriate support salt in consideration of the type of added basic axis ligand.

On the other hand, since the electrochemical device uses oxygen as a positive electrode active material, when supplying this oxygen from outside air, it is important to know how to supply gas having high oxygen pressure with high efficiency in the device. . A partition wall made of the above-described oxygen permeable membrane or oxygen permeable material is disposed at an air intake port through which air can be blown into the anode from the outside, and oxygen is supplied through the partition wall, that is, through an oxygen permeable membrane or oxygen permeable material. Can.

As described above, the oxygen-permeable membrane or oxygen-permeable material disposed at this air inlet has a high content of cobalt porphyrin complex capable of selectively binding to oxygen, and the cobalt porphyrin complex itself is also coordinated by a basic axis ligand to cobalt. As a result, the selective permeability of oxygen becomes an improved polymer compound, and therefore it is possible to selectively permeate a large amount of oxygen. The gas having a high oxygen partial pressure can be stably supplied to the device by disposing such an oxygen-permeable membrane or an oxygen-permeable material at the air intake of the battery.

Therefore, the electrochemical device can exhibit good electrochemical properties. In addition, it is possible to increase the oxygen concentration in the air supplied to the device by using the oxygen-permeable membrane or the oxygen-permeable material as a partition wall on the air-intake side of the device, and it is possible to reduce the overvoltage of the redox reaction. Ideally, in a two-electron reaction, if the oxygen concentration in the air is set to 21%, and the shift factor is 25?, the overvoltage of 40 mV is at least predicted, but the activation process is Due to the complexity, the actual overvoltage is greater).

Next, the present invention using examples will be described in more detail, but the present invention is not limited to the following implementations.

[Example]

(Production and evaluation of oxygen permeable materials)

First, an oxygen permeable membrane was synthesized by the method shown below.

[Example 1: Preparation of oxygen permeable membrane]

As a cobalt porphyrin complex, a complex for cobalt distribution to tetraphenylporphyrin having one acetoacetate group is used, a basic axial ligand is used as the acrylate compound, and tetrafunctional acrylate is used as the acrylate compound, and the polymer compound is subjected to a Michael type addition reaction. Was synthesized.

Specifically, first, as shown in the reaction scheme 2 of the following <Formula 9>, a monomer (acetoacetate-substituted porphyrin) having an acetoacetate group serving as a Michael donor introduced into tetraphenylporphyrin was synthesized.

100 mg (0.15 mmol) of 5-(4-methoxycarbonylphenyl)-10,15,20-triphenylporphyrin was dissolved in a mixed solvent of DMF/chloroform, a small amount of lutidine was added, and then cobalt chloride hexahydrate ( 141 mg, 0.6 mmol, 4eq) was added, and the mixture was stirred under nitrogen atmosphere at 50? for 12 hours. After reprecipitation purification, a purple powder 2 (Co) was obtained (77 mg, yield 70%). The introduction of cobalt was suggested because the peak of Q band decreased from 4 to 2 specific to the metal complex by the UV spectrum. Cobalt porphyrin 2 (Co) (50 mg, 0.068 mmol) and lithium aluminum hydride (5.2 mg, 0.14 mmol) were dissolved in THF, stirred under nitrogen atmosphere at room temperature for 1 hour, and subjected to column purification to obtain 3 (as a purple powder). Co) was obtained (25.8 mg, yield 59%). 3(Co) was dissolved in (23mg, 0.033mmol) toluene, diketen (4.2mg, 0.045mmol, 1.5eq), and TEA were added, followed by stirring at room temperature overnight. After stirring, through column purification, an acetoacetate group-introduced cobalt porphyrin complex (acetoacetate-substituted cobalt porphyrin) was obtained as a red-violet powder 1 (Co) (8.3 mg, yield 27%).

<Formula 9>

(Reaction scheme 2)

Next, using the cobalt porphyrin complex synthesized above, an oxygen permeable membrane including a cobalt porphyrin complex was prepared by a Michael-type reaction.

In order to impart mechanical strength to the oxygen permeable membrane, an oxygen permeable membrane including a cobalt porphyrin complex was prepared on the support membrane. As the support film, a polypropylene film (Cellguard #2400, #3501) insoluble in a solvent at the time of film formation was used without inhibiting gas permeation. Specifically, at a concentration of 14 g/L, poly(1-trimethylsilyl-1-propine) was dissolved in toluene, sufficiently stirred and completely dissolved, followed by a bar coater method on a supporting film (Cellguard #2400). And dried for 24 hours. Subsequently, the acetoacetate-substituted cobalt porphyrin 1 (Co) 1 synthesized in the above was dissolved in 5 mg (1 equivalent), 0.25 ml of chloroform, and 2 equivalents of methylimidazole or benzylimidazole was added and stirred sufficiently. After stirring, 1.25 equivalents of tetrafunctional acrylate, 1.5 equivalents of t-butyl acetoacetate and 1, 8-diazabicyclo(5,4,0)-undecene (DBU) as catalyst, 20% by weight relative to porphyrin 1 It was added, dissolved in chloroform, and formed on a poly(1-trimethylsilyl-1-propene) film of a supporting film at room temperature by a bar coater method, followed by drying and curing for 1 day to prepare an oxygen permeable film.

If the 1R spectrum measurement is performed before and after curing, as shown in Fig. 3 (the solid line in Fig. 3 shows the spectrum after curing and the broken line after curing), the absorption band around 790 cm ^-1 resulting from C=C angular vibration. Since the decrease was observed, the progress of the Michael-type addition reaction of acetoacetate-substituted cobalt porphyrin 1 (Co) was suggested even on the supporting membrane. Moreover, the reaction conversion rate of the acrylic group calculated from the area of the absorption band near 790 cm ^-1 was 76%. The content of porphyrin in the cobalt porphyrin complex is up to 70% by weight.

[Comparative Example 1: Preparation of oxygen permeable membrane]

As a cobalt porphyrin complex, a complex for cobalt distribution to tetraphenylporphyrin having one acetoacetate group is used, a basic axial ligand is used as the acrylate compound, and tetrafunctional acrylate is used as the acrylate compound, and the polymer compound is subjected to a Michael type addition reaction. Was synthesized.

Specifically, first, as shown in the reaction scheme 2 of the following <Formula 9>, a monomer (acetoacetate-substituted porphyrin) having an acetoacetate group serving as a Michael donor introduced into tetraphenylporphyrin was synthesized.

100 mg (0.15 mmol) of 5-(4-methoxycarbonylphenyl)-10,15,20-triphenylporphyrin was dissolved in a mixed solvent of DMF/chloroform, a small amount of lutidine was added, and then cobalt chloride hexahydrate ( 141 mg, 0.6 mmol, 4eq) was added, and the mixture was stirred under nitrogen atmosphere at 50? for 12 hours. After reprecipitation purification, a purple powder 2 (Co) was obtained (77 mg, yield 70%). The introduction of cobalt was suggested because the peak of Q band decreased from 4 to 2 specific to the metal complex by the UV spectrum. Cobalt porphyrin 2 (Co) (50 mg, 0.068 mmol) and lithium aluminum hydride (5.2 mg, 0.14 mmol) were dissolved in THF, stirred under nitrogen atmosphere at room temperature for 1 hour, and subjected to column purification to obtain 3 (as a purple powder). Co) was obtained (25.8 mg, yield 59%). 3(Co) was dissolved in (23mg, 0.033mmol) toluene, diketen (4.2mg, 0.045mmol, 1.5eq), and TEA were added, followed by stirring at room temperature overnight. After stirring, through column purification, an acetoacetate group-introduced cobalt porphyrin complex (acetoacetate-substituted cobalt porphyrin) was obtained as a red-violet powder 1 (Co) (8.3 mg, yield 27%).

<Formula 9>

(Reaction scheme 2)

Next, using the cobalt porphyrin complex synthesized above, an oxygen permeable membrane including a cobalt porphyrin complex was prepared by a Michael-type reaction.

In order to impart mechanical strength to the oxygen permeable membrane, an oxygen permeable membrane including a cobalt porphyrin complex was prepared on the support membrane. As the support film, a polypropylene film (Cellguard #2400, #3501) insoluble in a solvent at the time of film formation was used without inhibiting gas permeation. Specifically, at a concentration of 14 g/L, poly(1-trimethylsilyl-1-propine) was dissolved in toluene, sufficiently stirred and completely dissolved, followed by a bar coater method on a supporting film (Cellguard #2400). And dried for 24 hours. Subsequently, the acetoacetate-substituted cobalt porphyrin 1 (Co) 1 synthesized in the above was dissolved in 5 mg (1 eq.) and 0.25 ml of chloroform and stirred sufficiently. After stirring, 1.25 equivalents of tetrafunctional acrylate, 1.5 equivalents of t-butyl acetoacetate and 1, 8-diazabicyclo(5,4,0)-undecene (DBU) as catalyst, 20% by weight relative to porphyrin 1 It was added, dissolved in chloroform, and formed on a poly(1-trimethylsilyl-1-propene) film of a supporting film at room temperature by a bar coater method, followed by drying and curing for 1 day to prepare an oxygen permeable film.

[Example 2: Preparation of oxygen permeable material]

An oxygen permeable material in which the oxygen permeable membrane of Example 1 was formed on a porous substrate was prepared. Specifically, a hydrophilic polypropylene film (Cell Guard #2400: film thickness 25 µm, pore diameter 0.125 ｘ 0.05 µm, cell guard #3051: film thickness 25 µm) was selected as the porous substrate (porous support film). The polypropylene film has a property of not allowing water that has passed through the gas to pass through, and a porphyrin solution can be uniformly applied on the support film without the need to calculate the chloroform solution. Acetoacetate-substituted cobalt porphyrin 1 (Co) (Mw: 785.8, 10 mg) and tetrafunctional acrylate 2 (Mw: 352.4, 2.5 mg, 0.5 eq) shown in (Reaction Scheme 3) above, and 1% by weight of DBU It was dissolved in 0.2 mL chloroform, deposited on a porous support membrane (6 cm ｘ 6 cm) by a bar coater method, and cured at room temperature for 12 hours to prepare an oxygen permeable membrane. Even after curing, peeling and the like from the porous support film were not found, and an oxygen permeable material was prepared in which an oxygen permeable film containing 80% by weight of a cobalt porphyrin complex was formed on the porous support film.

[Comparative Example 2: Preparation of oxygen permeable material]

An oxygen permeable material was manufactured in the same manner as in Example 2, except that the oxygen permeable membrane of Example 2 was used instead of the oxygen permeable membrane of Example 1.

[Evaluation of oxygen permeation performance]

The permeation coefficient P of the gas can be expressed by the volume of the diffusion coefficient D and the solubility coefficient S. The transmission coefficient P can be obtained as an intrinsic value that does not depend on the film area and the film thickness, based on the following equation [Formula 1]. On the other hand, in the following [Equation 1], the permeate flow rate Q [cm ³ ], diffusion coefficient D [cm ² s ^-1 ], solubility S [cm ³ (STP) cm ^-3 cmHg], film thickness 1 [ Cm], cross-sectional area A[cm ² ], pressure difference ?p[cmHg].

[Equation 1]

The oxygen permeable membranes of Example 1 and Comparative Example 1 were measured by a pressure method using a beam flux meter (BFM). In this apparatus, gas (oxygen and nitrogen) is permeated by applying pressure from the top of the membrane, and the time required for the gas to permeate per unit volume is calculated. In this method, the permeation amount of pure gas can be measured, and a film weakened by thin film and high-concentration complex loading, or a film obtained by casting a glass polymer film or the like on a support film is appropriately measured. Compared to other measurement methods (low vacuum method, electrode method, etc.), the transmittance can be measured with a very small amount of sample, and listed as an advantage that the measurement does not take time.

4A shows a characteristic diagram showing the relationship between the differential pressure (p ₁ -p ₂ : horizontal axis) of oxygen and nitrogen and the oxygen transmission coefficient (P: vertical axis) of oxygen in the oxygen permeable membrane of Comparative Example 1 (● : Oxygen permeation coefficient, ○: Nitrogen permeation coefficient), FIG. 4B, in the oxygen permeation membrane of Example 1, the differential pressure between oxygen and nitrogen (p ₁ -p ₂ : horizontal axis) and oxygen permeation coefficient (P: It shows the characteristic diagram showing the relationship with (the vertical axis) (●: oxygen permeation coefficient, ○: nitrogen permeation coefficient).

4A and 4B, due to the presence or absence of a basic axial ligand for the cobalt porphyrin complex, a difference in the permeability of oxygen and nitrogen was remarkable at a pressure difference of about oxygen partial pressure (about 15 cmHg) in the atmosphere. . That is, the difference between the permeability of oxygen and nitrogen in the oxygen-permeable film of Comparative Example 1 is that oxygen is about "1.4" greater than nitrogen, and the difference between the permeability of oxygen and nitrogen in the oxygen-permeable film of Example 1 is, Oxygen increases to "5" or more at a time with respect to nitrogen. As described above, as the basic axial ligand is toasted with the metal porphyrin derivative, the selective permeability of oxygen can be maintained without deterioration even in an environment having an oxygen partial pressure or higher in the air.

In the above, the most suitable embodiments of the present invention will be described in detail with reference to the accompanying drawings, but the present invention is not limited to the related examples. Those of ordinary skill in the art to which the present invention pertains are apparent within the scope of the technical spirit described in the claims, and it is clear that various modifications or amendments may have an idea, and of course, the present invention It can be understood as belonging to the technical scope of.

For example, in the above-described embodiment, the case where the electrochemical device is a metal-air battery is listed and described as an example, but is not limited to these. For example, the electrochemical device according to the present invention includes oxygen, such as a fuel cell. It may be a battery used for the redox reaction.

On the other hand, a metal porphyrin derivative in which a transition metal such as copper is assigned to a tetraphenylporphyrin derivative and a tetraphenylporphyrin derivative, for example, a metal porphyrin complex, has a selective oxygen permeability, although not as much as a cobalt complex.

100: lithium air battery 110: positive electrode
111: current collector 112: catalyst layer
120: cathode 130: electrolyte

Claims (20)

A polyfunctional acrylate-based compound and a metal porphyrin derivative are bonded to each other to include a crosslinked backbone,
The polyfunctional acrylate-based compound is a short-chain acrylate-based compound having 20 or more carbon atoms,
The metal porphyrin derivative is a complex in which cobalt is coordinated to the tetraphenylporphyrin derivative represented by the following Chemical Formula 1,
A polymer compound coordinated by a basic axis ligand at the fifth position of the cobalt:
<Formula 1>

In Chemical Formula 1,
R ₁ , R ₂ , R ₃ and R ₄ are independently of each other an amino group, acetoacetate group, acetoacetamide group, cyanoacetate group, cyanoacetamide group, hydrogen , Halogen group, substituted or unsubstituted C1-C10 alkyl group, substituted or unsubstituted C2-C10 alkenyl group, substituted or unsubstituted C2-C10 alkynyl group, substituted or unsubstituted C6-C10 aryl group, or a combination thereof Is a combination,
However, at least one of R ₁ , R ₂ , R ₃ and R ₄ is an amino group, acetoacetate group, acetoacetamide group, cyanoacetate group, or cyanoacetamide ) Group. The method of claim 1, wherein the metal porphyrin derivative is a polymer compound capable of coordinating oxygen molecules to a sixth position located on the opposite side of the metal. The polymer compound according to claim 1, wherein the basic axis ligand comprises a nitrogen-containing organic ligand. The polymer compound of claim 1, wherein the polyfunctional acrylate-based compound and the metal porphyrin derivative are bonded to each other by a Michael-type addition reaction and crosslinked. The method of claim 1, wherein the metal porphyrin derivative contains at least one nucleophilic functional group, and part or all of the nucleophilic functional group and the acryl group included in the polyfunctional acrylate compound are bonded to each other by Michael type addition reaction. A polymer compound comprising a crosslinked backbone. The polymer compound according to claim 1, wherein a site derived from the metal porphyrin derivative is present in a main chain or a pendant group of the backbone. delete The polymer compound according to claim 1, wherein the content of the metal porphyrin derivative per unit content of the polymer compound is 30% by weight or more. The polymer compound according to claim 1, wherein the polyfunctional acrylate-based compound comprises a bifunctional acrylate, a trifunctional acrylate, or a tetrafunctional acrylate. delete The polymer compound according to claim 1, wherein the polyfunctional acrylate-based compound comprises an alkylene group substituted with halogen. Oxygen permeable membrane using the polymer compound according to any one of claims 1 to 6, 8, 9, and 11. The oxygen-permeable membrane of claim 12, wherein the oxygen-permeable membrane comprises a composite oxygen-permeable membrane formed on a porous substrate or in pores of the porous substrate. The oxygen-permeable membrane according to claim 13, wherein the porous substrate is coated with a gas-permeable polymer membrane. 15. The method of claim 14, The gas-permeable polymer membrane is an oxygen permeable membrane formed of poly (1-trimethylsilylpropene). The oxygen-permeable membrane according to claim 13, wherein the oxygen-permeable membrane has an oxygen permeability coefficient with respect to a nitrogen permeability coefficient of at least 8 times at a pressure of 1 cmHg or more than 2 times at 50 cmHg. Anode using oxygen as a cathode active material,
A negative electrode that uses a material that can occlude and release lithium ions as a negative electrode active material,
An electrolyte disposed between the positive electrode and the negative electrode, and
It has a partition wall made of an oxygen-permeable membrane according to claim 12,
An electrochemical device that supplies oxygen to the anode via the partition wall. 18. The electrochemical device of claim 17, wherein the electrochemical device comprises an oxygen permeable membrane according to claim 13. 18. The electrochemical device of claim 17, wherein the electrochemical device is a lithium air battery. 18. The electrochemical device of claim 17, wherein the negative active material is lithium metal.

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