JP2014156569A - Phthalocyanine polymer and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phthalocyanine polymer obtained while having an unambiguous unit structure and a stable quality and a manufacturing method capable of easily synthesizing the same.SOLUTION: A high-Curie-point ferromagnetic phthalocyanine polymer is synthesized as a result of a Wurtzite reaction of high-chlorine-content iron (II)-phthalocyanine and an alkali metal K. Phthalocyanine 1 and potassium 2 are specifically vacuum-sealed into a silica glass tube 3. This silica glass tube 3 is placed within a box-shaped electric furnace and then heated. This heating operation is carried out according to the trapezoidal heating pattern shown in the graph of Figure 6, and after the temperature within the electric furnace has reached 400°C, the temperature is maintained at 400°C for 12 hours. Subsequently, the reaction product is poured into water and agitated. A byproduct alkali metal salt KCl is removed by means of centrifugal separation or filtration. The targeted phthalocyanine polymer is then obtained by means of vacuum drying.

Description

  The present invention relates to a novel phthalocyanine polymer and a method for producing the same.

Phthalocyanine forms a complex with a metal ion to form a blue organometallic complex, and is used as a multifunctional material such as a blue paint, an organic solar cell, and an optical recording medium. FIG. 1 is a perspective view showing the molecular structure of this phthalocyanine, and its chemical formula is represented as C ₃₂ H ₁₆ N ₈ M. In this chemical formula, M is an ion of a transition metal or a typical element. Phthalocyanine is thermally, light, and chemically stable, and becomes a light material by blue light emission by the π electrons, and becomes a semiconductor material by its p-type semiconductor characteristics. Moreover, although it is few as an application example, it also becomes a magnetic material by the magnetic moment by the central metal.

  Phthalocyanine has a very low Curie temperature due to the weak exchange magnetic interaction between molecules. For example, manganese phthalocyanine (β-MnPc) having a β crystal form is a molecule whose molecular orbitals are shown as long ellipses parallel to each other in the structural perspective view shown in FIG. The exchange magnetic interaction between them is weak. The graph of FIG. 3 shows the magnetic characteristics of this manganese phthalocyanine with respect to temperature. The horizontal axis of the graph represents the Kelvin temperature T [K], and the vertical axis represents the magnetic susceptibility χ [emu / g]. As shown in the graph, manganese phthalocyanine has an extremely low Curie temperature Tc of 8.6 [K] and does not exhibit magnetism at room temperature of about 300 [K] (= 26.85 [° C.]) indicated by an arrow.

  However, in the phthalocyanine polymer represented by the fused-ring type sheet polymer shown in FIG. 4, the exchange magnetic interaction between molecules is strengthened by the extension of the molecular orbitals, and the electrons of the transition metal ions M at the center of each phthalocyanine molecule. The direction of spin is aligned as shown by arrows, and the magnetic properties may be greatly improved. In this sheet polymer, each phthalocyanine molecule is bonded via a shared benzene ring A.

Conventionally, a method disclosed in Non-Patent Document 1 is known as a method for synthesizing a phthalocyanine polymer. Non-Patent Document 1 discloses the following reaction formula (1).

  In the reaction formula (1), M represents a transition metal element or the like. Reaction formula (1) represents that a fused-ring phthalocyanine polymer is produced by synthesizing two tetracyanobenzenes (TCB) and one M.

  In addition, Patent Document 1 discloses that amorphous and crystalline potassium are doped by evaporating purified iron (II) phthalocyanine and the like and metal potassium, reacting both in a gas phase and cooling to room temperature. It is disclosed that iron phthalocyanine and the like are synthesized. This document describes that this organic magnetic material exhibits ferromagnetism at room temperature and includes an amorphous part, so that there is no deterioration in magnetic properties in air.

D. Wohrle et al., Makromol. Chem. 186, 2209 (1985)

JP-A-10-208914

  However, in the conventional synthesis method disclosed in Non-Patent Document 1, the characteristics of the product are different due to slight differences in synthesis conditions, and the quality of the obtained phthalocyanine polymer is not stable. Further, a fused-ring phthalocyanine polymer obtained by the above synthesis method, for example, a polymer of manganese phthalocyanine, shows a response to a permanent magnet at room temperature. However, its magnetic characteristics with respect to temperature change show a characteristic that the magnetization decreases gently with increasing temperature, and does not show the characteristic of a single ferromagnetic material whose magnetization decreases rapidly at the Curie temperature with increasing temperature. . This result indicates that the product is a mixture of a plurality of ferromagnetic polymers having different Curie temperatures.

  Moreover, the magnetic material containing an amorphous part disclosed by the above-mentioned conventional patent document 1 changes variously according to the substance, composition, etc. which the manufacturing method selects, as described in the same document. That is, it is necessary to carry out an appropriate reaction temperature, reaction time, cooling rate after reaction, heat treatment, and the like for each substance and composition to be selected. For this reason, it is difficult to industrially mass-produce the magnetic material disclosed in Patent Document 1 with stable quality.

  Pure organic molecular ferromagnets such as b-phase p-NPNN are composed only of light elements such as carbon, nitrogen and hydrogen, and are composed of elements around us. For this reason, the raw material is inexpensive, but it requires complicated synthesis procedures, has a low Curie temperature of about a few [K], and has a low saturation magnetization value, making it suitable for practical use as a magnetic material. Not.

  In addition, polymer ferromagnets such as pyrolytic carbon containing carbon as a main component have been developed and exhibit ferromagnetism at room temperature, but have a small magnetization value and weak magnetism, and are similarly impractical. Also, its structure is not clear.

The present invention has been made to solve such problems,
A phthalocyanine molecule having a transition metal as a central metal or a metal-free phthalocyanine molecule as a structural unit, and a polymer is formed by bonding of carbon atoms constituting the phthalocyanine molecule, for example, the following general formula (2) (wherein M Represents a transition metal element or H ₂ ).

を構成する外側の炭素原子が、隣接する同様なフタロシアニン分子を構成する外側の炭素原子との間で、炭素原子どうしの結合Ａ^１〜Ａ^１６を形成する。 The phthalocyanine polymer provided by this configuration is, for example, a phthalocyanine molecule represented by the following general formula (3)

The carbon atoms on the outside form a bond A ^{1 to} A ¹⁶ between carbon atoms with the outside carbon atoms that make up a similar phthalocyanine molecule adjacent to each other.

The following formula (4) shows a part of the combined state.

  Since the phthalocyanine polymer provided by this configuration is composed of phthalocyanine molecules as a unit, the unit structure is clear and easy to synthesize, is obtained with stable quality, and has extremely high practicality. In addition, a polymer of phthalocyanine molecules having a transition metal as a central metal exhibits the properties of a single ferromagnetic material whose magnetization sharply decreases at a very high Curie temperature compared to other organic ferromagnetic materials at room temperature. Moreover, the magnetization specific to phthalocyanine is very large.

とアルカリ金属とを、真空中または不活性ガス中で、例えば３５０℃〜５００℃の温度で加熱することで反応させて、フタロシアニン分子の重合体を合成するフタロシアニン重合体の製造方法を構成した。 Further, the present invention relates to the following general formula (5) (wherein M represents a transition metal element or H ₂ , R ^{1 to} R ¹⁶ represent halogen atoms, and R ^{1 to} R ¹⁶ are mixed with hydrogen atoms. Compound)

A phthalocyanine polymer production method for synthesizing a polymer of phthalocyanine molecules by reacting an alkali metal with a alkali metal in a vacuum or an inert gas by heating at a temperature of, for example, 350 ° C. to 500 ° C.

  According to this configuration, only the uniform conditions of heating can be performed without performing the appropriate reaction temperature, reaction time, cooling rate after the reaction, heat treatment, etc. Thus, the phthalocyanine polymer can be easily synthesized. For this reason, it becomes possible to industrially mass-produce the phthalocyanine polymer with stable quality. When synthesizing polymers of phthalocyanine molecules with transition metal as the central metal, it is possible to industrially mass-produce organic magnetic materials with a Curie temperature higher than room temperature and exhibiting ferromagnetism at room temperature with stable quality. It becomes.

  In the present invention, the compound represented by the general formula (5) and the alkali metal are in a molar ratio of 1 to X or more (X is the number of halogens per molecule of the compound represented by the general formula (5)). It is made to react.

  According to this structure, an alkali metal can be reacted with each of all halogens contained in the compound represented by the general formula (5). Therefore, the reactivity is very high and the polymerization is easy. Residual alkali metals that cause deterioration of the material can be completely removed by washing with water or the like.

  In addition, the present invention is characterized in that an alkali metal salt by-product produced by the reaction between a halogen and an alkali metal is removed by washing with water and then dried to obtain a phthalocyanine polymer.

  According to the manufacturing method of this structure, the alkali metal salt by-product produced | generated by reaction of a halogen and an alkali metal can be removed by simple process which only dries after washing with water.

  According to the present invention, as described above, a phthalocyanine polymer having a clear unit structure, easy synthesis, stable quality, and extremely high practicality is provided. Also provided is a phthalocyanine polymer having a very large magnetization and having a Curie temperature higher than room temperature and exhibiting the properties of a ferromagnetic substance alone. Moreover, the manufacturing method of the phthalocyanine polymer which can synthesize | combine this phthalocyanine polymer simply by uniform conditions of a heating is provided.

It is a perspective view which shows the molecular structure of phthalocyanine. It is a perspective view which shows the structure of manganese phthalocyanine ((beta) -MnPc) which has (beta) crystal type. It is a graph which shows the magnetic characteristic with respect to the temperature of manganese phthalocyanine. 1 is a plan view showing the structure of a fused-ring type sheet polymer of phthalocyanine. It is process drawing which shows the manufacturing method of the high Curie temperature ferromagnetic phthalocyanine polymer by one embodiment of this invention. It is a graph which shows the heating pattern in the manufacturing method shown in FIG. It is a graph which shows each X-ray-diffraction result of the reaction material just after the heat processing in the manufacturing method shown in FIG. 5, and the reaction material after the washing process with water and nitric acid. It is an electron micrograph of the reaction material after the washing process with water and nitric acid in the manufacturing method shown in FIG. It is a graph which shows the result of having measured the magnetization curve of the high Curie temperature ferromagnetic phthalocyanine polymer by one embodiment of this invention. It is a graph which shows the result of having measured Curie temperature _Tc of the high Curie temperature ferromagnetic phthalocyanine polymer by one embodiment of this invention.

  Next, an embodiment of a phthalocyanine polymer and a method for producing the same according to the present invention will be described.

In the present embodiment, a high Curie temperature ferromagnetic phthalocyanine polymer is synthesized using high chlorinated iron (II) phthalocyanine as the compound represented by the general formula (5) and potassium K as the alkali metal. This synthesis is performed by a Wurtz reaction represented by the following formula (6) between highly chlorinated iron (II) phthalocyanine and potassium K.

As represented by the above formula (6), the high chlorinated iron (II) phthalocyanine is composed of iron Fe in which M in the general formula (5) is a transition metal element, and 16 substituents R ^{1 to} R ¹⁶ are Expressed as chlorine Cl. The synthesis is performed by reacting a high chlorinated iron (II) phthalocyanine with a molar ratio of 1 and potassium K at a molar ratio of 16 to produce a polymer of iron phthalocyanine molecules and 16 alkali metal salts KCl.

  A specific method of synthesis is shown in FIG. 5. First, as shown in FIG. 5A, high chlorinated iron (II) phthalocyanine 1 and potassium 2 are vacuum sealed in a silica glass tube 3. And this silica glass tube 3 is put into a box type electric furnace and heated. This heating is performed in a trapezoidal heating pattern shown in the graph of FIG. In the graph, the horizontal axis indicates time, and the vertical axis indicates the temperature in the electric furnace. The temperature in the electric furnace is maintained at 400 ° C. for 12 hours after reaching 400 ° C.

  When the silica glass tube 3 is heated to 400 ° C., the highly chlorinated iron (II) phthalocyanine 1 and potassium 2 in the silica glass tube 3 are melted to form a reaction product in a black mass. As shown in FIG. 5B, this reaction product is placed in water and stirred, and centrifuged or filtered to remove the alkali metal salt KCl as a by-product.

In this embodiment, thereafter, as shown in FIG. 3C, the reaction product from which the alkali metal salt KCl has been removed is stirred in a 20% HNO ₃ aqueous solution and centrifuged, whereby iron in the phthalocyanine 1 is obtained. When liberated, the removal operation was performed in order to eliminate the influence on the magnetism.

  Thereafter, as shown in FIG. 4D, the reaction product was stirred in water, centrifuged, and vacuum-dried to obtain a black and powdery iron phthalocyanine polymer.

FIG. 7 is a graph showing the X-ray diffraction result of how much intensity of the X-ray beam is detected with respect to the diffraction angle 2θ [deg.] When X-rays are incident on the reactant from one direction. The horizontal axis of the graph represents the diffraction angle 2θ [deg.], And the vertical axis represents the diffraction intensity (Intensity) [cps] of the X-ray beam. Moreover, the measurement result (a) in the graph is a reaction product immediately after the reaction by the heat treatment in the silica glass tube 3 shown in FIG. 5 (a), and the measurement result (b) is shown in FIG. 5 (b). washing treatment with water, and represents the measurement results for the reaction product after completion of the cleaning process with 20% HNO ₃ aqueous solution shown in FIG. 5 (c).

As shown in the graph, in the measurement result (a) immediately after the reaction, diffraction intensity peaks appear in some places due to the presence of the by-product alkali metal salt KCl. However, in the measurement result (b) after washing in water and a 20% HNO ₃ aqueous solution, such a diffraction result due to the alkali metal salt KCl does not appear, and a gentle mountain peak due to the phthalocyanine polymer is present. Appears in the diffraction intensity. This confirms that the alkali metal salt KCl has been removed by washing in water and 20% HNO ₃ aqueous solution.

FIG. 8 is an electron micrograph of the reaction product after washing in water and 20% aqueous HNO ₃ solution. In the scale, the length of the line segment shown in the figure is 100 [nm], and an amorphous polymer of a phthalocyanine polymer is observed in the electron micrograph, and no precipitation of metallic iron fine particles is confirmed. For this reason, it is confirmed that the magnetism described later expressed by the phthalocyanine polymer obtained by the present production method does not include magnetism due to free iron.

  In addition, the diffraction result of free iron does not appear also in the diffraction measurement result (a) immediately after the reaction in FIG. Further, in the manufacturing process shown in FIG. 5C, iron free metal was not detected. For this reason, the manufacturing process which liberates the iron shown in FIG.5 (c) performed in this Embodiment is unnecessary. That is, the iron phthalocyanine polymer can be obtained by vacuum drying immediately after washing with water and centrifuging to remove the by-product shown in FIG.

The structure of the obtained iron phthalocyanine polymer is represented by the following chemical formula (7), and M in the above-described formula (4) is replaced with iron Fe which is a transition metal element.

  This iron phthalocyanine polymer has a phthalocyanine molecule having Fe as a central metal as a structural unit, and forms a polymer by bonding of carbon atoms constituting the phthalocyanine molecule. In addition, this iron phthalocyanine polymer has a three-dimensional structure because the diffraction line indicating the existence of a long-range ordered structure cannot be seen by X-ray diffraction, and the layered structure in which sheets are laminated on an electron micrograph cannot be seen. This is different from the conventional planar sheet-like polymer in which phthalocyanine molecules are bonded via a shared benzene ring A shown in FIG.

FIG. 9 is a graph showing the results of measuring the magnetization curve of the iron phthalocyanine polymer thus obtained. The size of the magnetic field the horizontal axis was applied in the graph (Magnetic field) [10kOe], the intensity of the vertical axis is measured magnetization (Magnetization) the per unit structure of iron phthalocyanine polymer units Bohr magneton mu _B [ [mu] _B / fu]. Moreover, the measurement result (a) obtained by connecting the rhombus plots in the graph is the measurement result for the high chlorinated iron (II) phthalocyanine before polymerization, and the measurement result (b) obtained by connecting the circular plots. These are the measurement results for the iron phthalocyanine polymer after polymerization. These are the measurement results at room temperature of T = 300 [K].

  As shown in the measurement result (b) at room temperature of T = 300 [K] in the graph, the iron phthalocyanine polymer after polymerization exhibits the key-type characteristics of the ferromagnetic material and exhibits ferromagnetism at room temperature. Was confirmed. It was also confirmed that it had a large magnetization value and a small coercive force compared to other organic magnetic materials. Further, when a permanent magnet was brought close to the iron phthalocyanine polymer powder at room temperature, it was also confirmed that the iron phthalocyanine polymer powder was attracted to the permanent magnet.

FIG. 10 is a graph showing the results of measuring the Curie temperature _Tc of the iron phthalocyanine polymer obtained as described above in a circular plot. The horizontal axis of the graph is the Kelvin temperature (Temperature) [K], and the vertical axis is the measured magnetization intensity (Magnetization) per mole of iron phthalocyanine polymer unit structure as M [emu / mol]. It is a representation. During the measurement, a magnetic field H of 1 [kOe] was applied to the sample.

As shown by the solid line portion of the graph, at the temperature immediately before reaching the Curie temperature _Tc of 490 [K], the strength of magnetization decreases rapidly according to the power law. This temperature dependence of magnetization is characteristic of ferromagnetic materials. From this measurement, it was confirmed that the iron phthalocyanine polymer had a Curie temperature _Tc of 490 [K] higher than room temperature of about 300 [K]. Note that the Curie temperature _Tc of metallic iron is 1043 [K].

As described above, according to the present embodiment, the ferromagnetic material has a characteristic that the magnetization sharply decreases at a very high Curie temperature _Tc compared to other organic ferromagnets. A very large phthalocyanine polymer is provided. Further, as represented by the chemical formulas (2) to (4), this phthalocyanine polymer is composed of phthalocyanine molecules as a unit, so that the unit structure is clear, synthesis is easy, and stable quality is obtained. And has extremely high practicality. On the other hand, the conventional polymer produced by the reaction represented by the above reaction formula (1) does not form an ideal sheet structure, and a mixture of polymers having various structures is produced. The unit structure of the phthalocyanine polymer became unclear, and the quality of the obtained ferromagnetic material was not stable.

In addition, according to the method for producing a phthalocyanine polymer according to the present embodiment, the conventional reaction temperature, reaction time, post-reaction cooling rate, heat treatment, etc. appropriate for each selected substance, composition, etc. Without performing the steps, a phthalocyanine polymer having a Curie temperature _Tc higher than room temperature can be easily synthesized under only the uniform heating conditions illustrated in FIG. Moreover, the by-product KCl produced by the reaction between the halogen Cl and the alkali metal K can be removed by a simple treatment in which the reaction product obtained by heating phthalocyanine and potassium K is washed with water and then dried. For this reason, it becomes possible to industrially mass-produce organic magnetic materials exhibiting ferromagnetism at room temperature with stable quality.

  In the production method of the present embodiment, since phthalocyanine is reacted at a molar ratio of 1 and potassium K is 16 at a molar ratio, each of the alkali metals with respect to 16 halogen Cls of phthalocyanine represented in the reaction formula (6). K can be reacted. Therefore, the reactivity is very high and the polymerization is easy. Residual alkali metal K that causes deterioration of the material can be completely removed by washing with water or the like.

In the above embodiment, the case where M in the formula represented by the general formula (2) is Fe as a transition metal element has been described. However, the transition metal element is not limited to Fe, and may be a transition metal element such as Ti, V, Cr, Mn, Co, Ni, and Cu. Alternatively, M in the formula represented by the general formula (2) may be H ₂ and metal-free phthalocyanine molecules may be polymerized in the same manner as in the above embodiment to produce a phthalocyanine polymer. Although this metal-free phthalocyanine polymer does not become a magnetic material, it is composed of phthalocyanine molecules as a unit. Therefore, like the transition metal phthalocyanine polymer according to the above embodiment, the unit structure is clear, easy to synthesize, and stable. And has extremely high practicality as a negative electrode material for lithium ion secondary batteries.

In addition, the halogen atoms R ^{1 to} R ¹⁶ in the formula represented by the general formula (5) are not limited to Cl, and may be halogen atoms such as F, Br, and I, for example. In addition, hydrogen atoms H may be mixed in the substituents R ^{1 to} R ¹⁶ . In the above embodiment, the case where K is used as the alkali metal has been described. However, the alkali metal is not limited to K, and may be an alkali metal such as Li, Na, Rb, or Cs.

  In the above embodiment, the case where phthalocyanine 1 and potassium 2 are vacuum-sealed in a silica glass tube 3 as shown in FIG. However, instead of vacuum sealing, an inert gas may be sealed in the silica glass tube 3 or heated by flowing an inert gas in an open system. Moreover, in said embodiment, although the heating temperature of the silica glass tube 3 was 400 degreeC, the heating temperature of the range of 350 to 500 degreeC may be sufficient.

Moreover, in the manufacturing method of said embodiment, the case where phthalocyanine was made to react by the molar ratio of 1 and potassium K was demonstrated. However, the phthalocyanine may be reacted at 1 and the alkali metal at a molar ratio of 16 or more. In addition, when hydrogen atoms H are mixed in the substituents R ^{1 to} R ¹⁶ , the compound represented by the general formula (5) and the alkali metal are paired with X or more (X is the general formula (5)). You may make it react by the molar ratio of the number of the halogens per molecule of the compound represented. According to this structure, an alkali metal can be reacted with each of all halogens contained in the compound represented by the general formula (5).

  Even with each of these configurations, the same effects as those of the above-described embodiment can be obtained.

  The transition metal phthalocyanine polymer obtained by this embodiment is a radio frequency blocking material, a radio wave absorbing material, a high frequency magnetic material such as a transformer, an organic spintronic material such as a magnetoresistive element or a Hall element, an electronic circuit printing material, It has applicability to a wide range of applications such as conductive paste materials, magnetic paste materials, and printer toner materials. Further, the metal-free phthalocyanine polymer obtained in the same manner as in this embodiment is useful as a negative electrode material for lithium ion secondary batteries.

1 ... high chlorinated iron (II) phthalocyanine 2 ... potassium K
3 ... Silica glass tube

Claims (6)

  A phthalocyanine polymer comprising a phthalocyanine molecule having a transition metal as a central metal or a metal-free phthalocyanine molecule as a constituent unit, and forming a polymer by bonding of carbon atoms constituting the phthalocyanine molecule. The following general formula (2)

The phthalocyanine polymer according to claim 1, wherein M represents a transition metal element or H ₂ . The following general formula (5)

(Wherein, M is a transition metal element or H ₂ , R ^{1 to} R ¹⁶ are halogen atoms, and R ^{1 to} R ¹⁶ may be mixed with hydrogen atoms) and an alkali metal A process for producing a phthalocyanine polymer in which a polymer of phthalocyanine molecules is synthesized by heating in a vacuum or in an inert gas.   Reacting the compound represented by the general formula (5) with an alkali metal at a molar ratio of 1 to X or more (X is the number of halogens per molecule of the compound represented by the general formula (5)). The method for producing a phthalocyanine polymer according to claim 3.   The method for producing a phthalocyanine polymer according to claim 3 or 4, wherein the heating is performed at a temperature of 350 ° C to 500 ° C.   6. The phthalocyanine polymer is obtained by removing the alkali metal salt by-product produced by the reaction between the halogen and the alkali metal by washing with water and then drying the product. The manufacturing method of the phthalocyanine polymer of any one.

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