JP2520135B2 - Polymer metal complex, method for producing the same, and polymer magnetic material comprising the complex - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel polymer metal complex, a method for producing the same, and a polymer magnetic material comprising the complex.
More specifically, the present invention is a polymer obtained by introducing a metal-containing porphyrin or a derivative thereof in which an organic compound having a central metal-coordinating atom is not substituted into a polymer main chain through an ester group. TECHNICAL FIELD The present invention relates to a metal complex, a method for extremely efficiently producing a polymer metal complex having a high metal content, and a polymer magnetic material comprising the complex, which is useful as a paramagnetic substance.

[Prior Art] Conventionally, as a polymer metal complex, for example, a metal-containing porphyrin nucleus is bound to a polymer main chain via a linking group such as an ester group or an amide group, and the porphyrin nucleus or the like has A covalent-bond type polymeric metal complex having an organic compound residue having an atom capable of coordinating with a metal and being covalently bonded has been proposed. (JP-A-54-117586
Issue).

However, in this covalent-bond polymer metal complex, as seen in Example 2 in the specification of the publication, the introduction rate of hemin is about 2%, and the content of the macrocyclic tetradentate planar ligand is high. It has the drawback of being few, and with regard to its use, its use as a catalyst material is only partially disclosed. Incidentally, the above-mentioned publication discloses a nitrogen atom, which is an atom capable of coordinating to a central metal, which is contained in an organic group bonded to a macrocyclic tetradentate planar ligand such as a porphyrin nucleus containing a metal, or a nitrogen atom. Absent.

By the way, in recent years, magnetic materials have made rapid progress with the development of electronics, and magnetic recording materials such as magnetic tapes have been widely used in fields such as video and audio. This magnetic recording material is conventionally formed by applying a magnetic powder such as a magnetic metal, an alloy, an intermetallic compound or a metal oxide onto a plastic film or disk such as polyethylene terephthalate.

However, the method of coating such a magnetic powder on a film or a disk has a drawback that coating unevenness is likely to occur and a limit to high recording density is inevitable.

Therefore, in order to improve such a defect, studies have been made to increase the recording density by imparting magnetism to a polymer that does not originally have magnetism and homogenizing the magnetic site.
Up to now, no practical polymer magnetic material has been found yet.

For example, it is conceivable to use the polymer complex described in the above publication for a recording material, but the introduction amount of the macrocyclic tetradentate planar ligand into the polymer main chain is too small, and it is difficult to introduce it in a large amount. However, it has been found that there is no characteristic as a magnetic material and therefore it cannot be used.

[Problems to be Solved by the Invention] Under the circumstances, the present invention is useful as an oxygen carrier and various chemical reaction catalysts, particularly as a paramagnetic material,
The object of the present invention is to provide a polymer metal complex obtained by introducing a metal-containing porphyrin into a polymer main chain, and a method for producing this polymer extremely efficiently.

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, introduced a large amount of metal-containing porphyrins into a polymer main chain through a specific linking group. It was found that the polymer metal complex having the paramagnetic property is easily obtained by polymerizing an acrylic polymerizable monomer having the metal-containing porphyrin bound through a specific linking group. The present invention has been completed based on this finding.

That is, the invention described in claim 1 for solving the above-mentioned problems is represented by the general formula (In the above general formula, R is hydrogen depletion or a methyl group, and PM is a metal-containing porphyrin residue or a metal-containing porphyrin derivative residue in which an organic compound residue having an atom capable of coordinating to a central metal is unsubstituted. And R ¹ is 2,3,7,8,1 on the pyrrole ring in the metal-containing porphyrin residue or the metal-containing porphyrin derivative residue.
An alkylene group bonded to at least one of the 2,13,17,18 positions, or a methine group in the metal-containing porphyrin residue or the metal-containing porphyrin derivative residue.
An unsubstituted or substituted aryl group bound to at least one of 5,10,15,20) and having a molecular weight of 5,000 to 100,0
The invention according to item 2, wherein the organic compound residue having an atom capable of coordinating to the central metal is unsubstituted and an ester-forming functional group is added. The first step of reacting the metal-containing porphyrin or its derivative with an acrylic acid compound to produce a polymerizable monomer that binds the metal-containing porphyrin or its derivative through an ester group, and polymerizing the polymerizable monomer. A method for producing a polymer metal complex having a repeating unit represented by the above general formula, characterized in that it comprises a second step of The organic compound residue that has been substituted and a porphyrin having an ester-forming functional group or a derivative thereof and an acrylic acid-based compound are reacted to form an ester. After obtaining an acrylic acid derivative that binds the porphyrin or a derivative thereof via a group, a first step of producing a polymerizable monomer by introducing a metal into the porphyrin residue, and a step of polymerizing the polymerizable monomer A method for producing a polymer metal complex having a repeating unit represented by the above general formula, which comprises two steps, wherein the invention described in item 4 has an ester group in the polymer main chain, A polymer magnetic material comprising a polymer-metal complex into which a metal-containing porphyrin and / or its derivative in which an organic compound residue having an atom capable of coordinating to a central metal is not substituted, The invention according to item 5 is the polymer magnetic material according to item 4, wherein the polymer complex has a repeating unit represented by the general formula in the molecule.

 Hereinafter, the present invention will be described in detail.

The polymer metal complex of the present invention is one in which a metal-containing porphyrin or a derivative thereof in which an organic compound residue having an atom capable of coordinating to a central metal is unsubstituted is introduced into a polymer main chain through an ester group. Therefore, the polymer may be a homopolymer or a copolymer, but in the molecule, (In the above general formula, R represents a hydrogen atom or a methyl group, and PM represents a metal-containing porphyrin residue or a metal-containing porphyrin derivative residue when an organic compound residue having an atom capable of coordinating to a central metal is unsubstituted. And R ¹ is 2,3,7,8,1 on the pyrrole ring in the metal-containing porphyrin residue or the metal-containing porphyrin derivative residue.
An alkylene group bonded to at least one of the 2,13,17,18 positions, or a methine group in the metal-containing porphyrin residue or the metal-containing porphyrin derivative residue.
Is a substituted or unsubstituted aryl group bonded to at least one of 5,10,15,20).

In the present invention, the metal coordinated to the central portion of the porphyrin ring in porphyrin or a derivative thereof is, for example, the 4th to 6th period IB of the periodic table.
Examples thereof include those selected from Group IIIB, Group IIB, Group V, Group VI, Group VII, Group VIII and rare earth metals. When used as a molecular magnetic material, among the above metals, vanadium,
Erbium, holmium, ytterbium, copper and manganese are preferred.

One kind of porphyrins containing these metals may be introduced into the polymer main chain, or two or more kinds of porphyrins containing different metals may be introduced in combination.
When the polymer metal complex is used as the polymer magnetic material, the metal content in the complex is preferably 50 mol% or more.

The porphyrin derivative used in the present invention is not particularly limited as long as it does not have a substituent having a coordinating atom of the central metal, for example, 2,3,7,8,12,13 on the pyrrole ring of porphyrin. Having a substituent such as an alkyl group in at least one of the 17,17,18 positions, or having a phenyl group having an unsubstituted or substituted group in at least one of the 5,10,15,20 positions of the methine group You can list things such as things.

Further, the molecular weight of the polymer metal complex is preferably selected in the range of 5,000 to 100,000 because if it is too small, the mechanical strength when formed into a film or the like will be low, and if it is too large, the moldability will deteriorate.

In the present invention, the polymer metal complex can be used as a polymer magnetic material having paramagnetism. For example, when the polymer metal complex is poly [chloro-5- (4-acryloyloxyphenyl) -10,15,20-triphenylporphinatomanganese (III)] [abbreviated as Poly AOTPPMn (III) Cl] The relationship among temperature, magnetic susceptibility and magnetic moment is as shown in FIGS. 1 and 2.
That is, from these figures, magnetic susceptibility [X _M ] and temperature [T]
The relationship with (K) almost satisfies the formula X _M = C / T (where C is a constant), and it can be seen that the complex exhibits paramagnetism.

When the polymer metal complex is poly [5- (4-acryloyloxyphenyl) -10,15,20-triphenylporphinato vanadyl (II)] [Poly AOTPPVO (II)], the temperature and magnetic susceptibility are The relationship with is as shown in FIG. As can be seen from this figure, when the VO (II) content in the complex is 50 mol%, the complex exhibits paramagnetism,
Shows antiferromagnetism.

According to the first method of the present invention, the polymer metal complex has
First, by reacting a metal-containing porphyrin having an ester-forming functional group with an acrylic acid-based compound while making a substituent having an atom capable of coordinating to a central metal unsubstituted
It can be produced by obtaining a polymerizable monomer that binds the metal-containing porphyrin via an ester group, and then polymerizing the polymerizable monomer.

According to the second method, first, a substituent having an atom capable of coordinating to a central metal is made unsubstituted, and a porphyrin having an ester-forming functional group is reacted with an acrylic acid-based compound to give an ester. After obtaining an acrylic acid derivative that binds the porphyrins via a group, a metal is introduced into the porphyrin residue to obtain a polymerizable monomer,
Then by polymerizing this polymerizable monomer,
It can be manufactured.

Examples of the acrylic acid compound include acrylic acid and methacrylic acid, or reactive derivatives thereof such as acrylic acid chloride, acrylic acid ester, methacrylic acid chloride, and methacrylic acid ester.

On the other hand, porphyrins or metal-containing porphyrins that are reacted with these acrylic acid-based compounds have a functional group that reacts with the acrylic acid-based compound to form an ester, and as the ester-forming functional group, , Usually a hydroxyl group.

Typical examples of the porphyrin having the ester-forming functional group include 5- (4-hydroxyphenyl) -10,15,
20-triphenylporphyrin (abbreviated as HOTPP) can be mentioned. This is benzaldehyde, p
It can be produced from hydroxybenzaldehyde and pyrrole.

In the present invention, a porphyrin having such an ester-forming functional group is introduced with a metal of a desired metal by using a salt of the desired metal and then reacted with the acrylic acid-based compound to prepare a polymerizable monomer. Alternatively, or after reacting a porphyrin having an ester-forming functional group with an acrylic acid-based compound, a metal is introduced into a porphyrin residue in the obtained acrylic acid-based derivative to prepare a polymerizable monomer. May be.

One example of a suitable method for reacting an ester-forming porphyrin or a metal-containing porphyrin with an acrylic acid-based compound is as follows. A suitable amount of the porphyrin or the metal-containing porphyrin and a triethylamine After dissolving the hydrogen chloride scavenger, a required amount of acrylic acid chloride or methacrylic acid chloride is added thereto, and the reaction is carried out at a normal temperature for about 1 to 30 hours. After completion of the reaction, the solvent and triethylamine hydrochloride are removed to obtain a crude product, which is then purified by using a chromatograph or the like to give an acrylic acid derivative in which a porphyrin or a metalloporphyrin is bound via an ester group. can get. When a metal-containing porphyrin is used in this reaction, the acrylic acid derivative can be used as it is as a polymerizable monomer in the next polymerization step, but when a metal-free porphyrin is used, It is necessary to perform an operation of introducing a desired metal into the porphyrin residue in the acrylic acid derivative.

In the present invention, the thus obtained polymerizable monomer to which the metal-containing porphyrins are bound via the ester group is polymerized in the next second step to obtain a desired polymer metal complex. This polymerization method is not particularly limited, and any method can be used from the methods conventionally used for the polymerization of acrylic acid-based monomers, but the radical polymerization method is usually preferably used.

Further, in the present invention, the polymerizable monomer may be homopolymerized, or two or more kinds of polymerizable monomers having different kinds of contained metals may be copolymerized, and the same kind of monomer containing no metal. Alternatively, it may be copolymerized with a copolymerizable monomer. By such a method, the kind and content of the metal in the polymer metal complex can be arbitrarily adjusted.

As the polymerization initiator used in the radical polymerization method, any one can be selected and used from those conventionally used for radical polymerization. Examples of such radical polymerization initiators include azo-based initiators such as azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanecarbonitrile, benzoyl peroxide, lauroyl peroxide, and di-t-dibutylperoxide. Oxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, peroxide initiators such as potassium persulfate, or hydrogen peroxide- Iron (II) salt,
Examples thereof include redox-based initiators such as persulfate-sodium hydrogen sulfite.

A preferred example of the method for producing a polymer metal complex by radical polymerization will be described. In a suitable solvent, for example, a solvent such as tetrahydrofuran, dimethylformamide, benzonitrile, etc. A copolymerizable monomer used accordingly is added, and the above-mentioned polymerization initiator is further added and dissolved, and polymerization is preferably carried out under reduced pressure at a temperature in the range of 40 to 100 ° C. The polymerization time varies depending on the type of monomer and temperature and cannot be determined unconditionally, but it is usually about 5 to 100 hours. If the polymerization temperature is lower than 40 ° C, the polymerization rate is too slow to be practical, and if it exceeds 100 ° C, the polymer chain tends to be difficult to extend, which is not preferable. The polymer metal complex thus produced can be isolated by a known means, and then, if necessary, recrystallized with a suitable solvent and purified.

Examples of the copolymerizable monomer include acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, acrylonitrile, styrene, α-methylstyrene, divinylbenzene, maleic anhydride, vinyl acetate, various α-olefins, Examples thereof include vinyl chloride. These monomers may be used alone or in combination of two or more.

The polymer metal complex of the present invention includes, in addition to the method of the present invention of homopolymerizing or copolymerizing the above-mentioned polymerizable monomer having a metal-containing porphyrin bound thereto, a polymerizable monomer having a metal-free porphyrin bound to Similar to the method, homopolymerized or copolymerized, through the ester group,
It can also be produced by a method in which a metal-free porphyrin is introduced into the polymer main chain and then a metal is introduced into the porphyrin residue of the polymer, or the polymer reaction is carried out. It can also be produced by a method of introducing a metal-containing porphyrin into the polymer main chain via an ester group. However, the method utilizing this polymer reaction is difficult to obtain a polymer metal complex having a high metal content, and is particularly disadvantageous for use as a polymer magnetic material.

[Advantages of the Invention] The polymer metal complex of the present invention is a novel one in which metal-containing porphines are introduced into the polymer main chain via an ester group, and is used as an oxygen carrier and various chemical reaction catalysts. It is useful. In particular, a polymer metal complex containing a metal in a large amount of, for example, 50 mol% or more exhibits paramagnetism and is useful as a magnetic recording material for video and audio. In addition, the polymeric metal complex is easy to mold and can be molded into any shape such as a film, a sheet, a sphere, or a column, depending on the application, which is extremely advantageous in practical use.

Further, according to the method of the present invention, an acrylic acid-based polymerizable monomer having a metal-containing porphyrin bound thereto is homopolymerized, two or more polymerizable monomers having different kinds of metals are copolymerized, or By means such as copolymerizing a monomer and a monomer that does not contain a copolymerizable metal, the kind and content of the metal in the obtained polymer metal complex can be arbitrarily adjusted,
A polymer metal complex having a high metal content, which cannot be obtained by a polymer reaction method, can be produced very easily.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples.
The present invention is not limited in any way by these examples.

(Synthesis Example 1) 5- (4-hydroxyphenyl) -10,15,20-triphenylporphinato vanadyl (II) [HOTPPVO (II)]
Synthesis of 5- (4-hydroxyphenyl) -10,15,20-triphenylporphyrin (HOTTP) 0.90 g and vanadium oxysulfate (VOSO ₄ · XH ₂ O) 2.10 g, DMF 300 ml, acetic acid 30 ml and trichloroacetic acid 10 ml After dissolving in a mixed solvent of and reacting under reflux (153 ° C.) for 7 hours, the solvent was removed to obtain a crude product.

Next, the crude product was dissolved in chloroform and chromatographed using a silica gel column (20 cm) to obtain HOTPPVO.
(II) After isolation, it was purified by recrystallization from a mixed solvent of chloroform-hexane. Yield 0.90g, 91% yield
Met.

(Synthesis Example 2) 5- (4-hydroxyphenyl) -10,15,20-triphenylporphinate erbium (III) [HOTPPEr (II
I) OH] synthesis HOTPP 0.50g and erbium chloride 6 moisture (ErCl ₃ 6H ₂
O) 0.50 g and imidazole 10 g are mixed and refluxed for 3 hours (2
50-260 ℃), and then mix the reaction mixture with chloroform (20m).
It was dissolved in a mixed solvent of 1 and 20 ml of methanol. This solution is filtered to remove insoluble matter, and the filtrate is washed with water.
After washing twice, the solvent was distilled off to obtain a crude product.

Then, this crude product was purified in the same manner as in Synthesis Example 1 to obtain HOTPPEr (III) OH 0.50 g (yield 77%).

(Synthesis Example 3) In the same manner as in Synthesis Example 2, 5- (4-hydroxyphenyl) -10,15,20-triphenylporphinatoholmium (III) [HOTPPYb (III) OH] was synthesized.

Example 1 0.89 g of HOTPPVO (II) obtained in Synthesis Example 1 and 1.0 g of triethylamine were dissolved in 80 ml of pyridine, and 0.5 g of acrylic acid chloride was added dropwise thereto over 5 minutes with stirring.
Then, stirring was continued for 12 hours at room temperature. Next, the reaction solution was filtered to remove triethylamine hydrochloride, and then the solvent was distilled off by a rotary evaporator to obtain a crude product. 5- (4-acryloyloxyphenyl) -10,15,20-triphenylporphinato vanadyl (II) [AOTPPVO (II)] was separated from this crude product using a silica gel column, followed by chloroform-hexane separation. Recrystallization was repeated using a mixed solvent for purification. Yield 0.43g,
The yield was 45%.

The results of infrared analysis and elemental analysis of this product are shown below.

IR (KBr): 1740cm ^-1 (νc = o), 1630cm ^-1 (νc =
c) Elemental analysis Next, a N-methyl-2pyrrolidone solution containing AOTPPVO (II) 14.30 × 10 ^-2 mol / dm ^-3 and azobisisobutyronitrile (AIBN) 1.83 × 10 ^-3 mol / dm ^-3 was added to a glass ampoule. The mixture was heated to 60 ° C. for 50 hours, the polymer was dissolved in chloroform, and then excess methanol was added thereto to isolate Poly AOTPPVO (III). Further, the procedure of dissolution-precipitation using chloroform-methanol was repeated 3 times for purification.

The yield of this product was 23.3%, and the weight average molecular weight Mw was
It was 8500. The elemental analysis values are shown below.

Elemental analysis value (Example 2) Example 1 was repeated except that methacrylic acid chloride was used instead of acrylic acid chloride in Example 1.
5- (4-methacryloyloxyphenyl) -10,15,20-triphenylporphinato vanadyl (II) [MAOTPPVO (II)] was produced in exactly the same manner as in. The yield of this monomer was 57%. The results of infrared analysis and elemental analysis of this monomer are shown below.

IR (KBr): 1740cm ^-1 (νc = o), 1640cm ^-1 (νc =
c) Elemental analysis Next, this MAOTPPVO (II) 17.46 × 10 ^-2 mol / dm ^-3 and AIB
A DMF solution containing N2.02 × 10 ⁻³ mol / dm ⁻³ was placed in an ampoule, and polymerization was carried out in the same manner as in Example 1 to obtain Poly MAOTPPVO.
(II) Obtained in a yield of 20.1%. Weight average molecular weight of this product
Mw is 8800, and the elemental analysis results are as follows.

Elemental analysis Example 3 0.50 g of HOTPPEr (III) OH obtained in Synthesis Example 2 and 0.30 g of triethylamine were dissolved in 50 ml of pyridine, and then 0.25 g of acrylic acid chloride was added dropwise to this solution over 5 minutes while stirring. And then continued stirring at room temperature for 12 hours.
Thereafter, the same treatment as in Example 1 was performed to obtain purified 5- (4-acryloyloxyphenyl) -10,15,20-triphenylporphinato erbium (III) [AOTPPEr (III) OH].
0.24 g was obtained (yield 43%).

The results of infrared analysis and elemental analysis of this monomer are shown below.

IR (KBr): 1740cm ^-1 (νc = o), 1630cm ^-1 (νc =
c) Elemental analysis Next, this AOTPPEr (III) OH5.14 × 10 ^-2 mol / dm ^-3 and AI
A benzonitrile solution containing BN2.44 × 10 ⁻³ mol / dm ⁻³ was placed in an ampoule, polymerization was carried out in the same manner as in Example 1, and Poly AOTPPEr (III) OH having a weight average molecular weight Mw of 8000 was 35.1.
Obtained in% yield. The elemental analysis results of this product are shown below.

Elemental analysis (Example 4) 5- (4-methacryloyloxyphenyl)-in the same manner as in Example 3 except that methacrylic acid chloride was used instead of acrylic acid chloride.
10,15,20-Triphenylporphinate erbium (II
I) [MAOTPPEr (III) OH] was obtained with a yield of 60%. The results of infrared analysis and elemental analysis of this product are shown below.

IR (KBr): 1740cm ^-1 (νc = o), 1630cm ^-1 (νc =
c) Elemental analysis Next, this MAOTPPEr (III) OH7.58 × 10 ^-2 mol / dm ^-3 and A
A benzonitrile solution containing IBN 1.35 × 10 ⁻³ mol / dm ⁻³ was placed in an ampoule, polymerization was carried out in the same manner as in Example 1, and Poly MAOTPPEr (III) OH having a weight average molecular weight Mw of 20,000 was 1%.
Obtained in a yield of 8.2%. The elemental analysis results of this product are shown below.

Elemental analysis Example 5 In the same manner as in the synthesis of AOTPPEr (III) OH of Example 3 from HOTPPHo (III) OH and acrylic acid chloride obtained in Synthesis Example 3, 5- (4-acryloyloxyphenyl)- 10,15,
20-Triphenylporphinatoholmium (III) [A
OTPPHo (III) OH] was obtained with a yield of 38%. The results of infrared analysis and elemental analysis of this monomer are shown below.

IR (KBr): 1740cm ^-1 (νc = o), 1640cm ^-1 (νc =
c) Elemental analysis Next, with this AOTPPHo (III) OH6.94 × 10 ^-2 mol / dm ^-3 ,
A benzonitrile solution containing AIBN 2.03 × 10 ⁻³ mol / dm ⁻³ was placed in an ampoule, and polymerization was carried out in the same manner as in Example 1 to obtain 6.4% of Poly AOTPPHo (III) OH having a weight average molecular weight of Mw7800. Got at a rate. The elemental analysis results of this product are shown below.

Elemental analysis Example 6 Using the HOTPPYb (III) OH obtained in Synthetic Example 3 and acrylic acid chloride in the same manner as in the synthesis of AOTPPEr (III) OH in Example 3, 5- (4-acryloyloxyphenyl)- 10,15,
20-triphenylporphiner totterbium (II
I) [AOTPPYb (III) OH] was obtained with a yield of 59%. The results of infrared analysis and elemental analysis of this product are shown below.

IR (KBr): 1740cm ^-1 (νc = o), 1630cm ^-1 (νc =
c) Elemental analysis Next, this AOTPPYb (III) OH 12.30 × 10 ^-1 mol / dm ^-3 and A
A benzonitrile solution containing IBN 2.14 × 10 ⁻³ mol / dm ⁻³ was placed in an ampoule, and polymerization was carried out in the same manner as in Example 1 to obtain Poly AOTPPYb (III) OH having a weight average molecular weight Mw8500 of 12.
Obtained at 3%. The elemental analysis results of this product are shown below.

Elemental analysis Example 7 5- (4-hydroxyphenyl) -10,15,20-triphenylporphyrin (HOTPP) 2.00 g and triethylamine
0.13 g was dissolved in 200 ml of tetrahydrofuran, 0.30 g of acrylic acid chloride was added dropwise to this solution over 20 minutes, and the mixture was stirred at room temperature for 2 hours. Thereafter, the same treatment as in Example 1 was performed to prepare 5- (4-acryloyloxyphenyl) -10,15,20-triphenylporphyrin (AOTPP).
1.53 g was obtained with a yield of 70% and an mp of 300 to 302 ° C. The results of infrared analysis and elemental analysis of this product are shown below.

IR (KBr): 1740cm ^-1 (νc = o), 1630cm ^-1 (νc =
c), 800 cm ⁻¹ (δc = c−H) Elemental analysis Next, this AOTPP 1.85 × 10 ^-2 mol / dm ^-3 and AIBN 1.21 × 10
A tetrahydrofuran solution containing ^-3 mol / dm ^-3 was placed in an ampoule and polymerized in the same manner as in Example 1 to obtain Poly AOTPP having a weight average molecular weight of Mw8000 at a conversion rate of 28.3%. The elemental results of this product are shown below.

Elemental analysis Next, 0.36 g of Poly AOTPP thus obtained and 0.36 g of manganese acetate were dissolved in 80 ml of DMF, and this was refluxed for 4 hours, and then the reaction-terminated liquid was added to an ice-cooled saturated NaCl aqueous solution. The precipitated greenish brown crystals were isolated by centrifugation and washed with 200 ml of water. This crystal was repeatedly recrystallized from a mixed solvent of benzene-hexane to give poly [chloro-5- (4-acryloyloxyphenyl) -10,15,20-
Triphenylporphinate manganese (III)] [Poly
AOTPPMn (III) cl] 0.34 g (yield 90%) was obtained. The elemental analysis results of this product are shown below.

Elemental analysis In this way, the weight average molecular weight Mw of 8,000 and 20,000 of 2
Various kinds of Poly AOT PPMn (III) Cl were prepared and their relations with temperature, magnetic susceptibility and magnetic moment were determined. The results are shown in FIGS. 1 and 2. From these figures Poly A
It can be seen that all of OTPPMn (III) Cl are paramagnetic substances.

(Example 8) Poly AOTPP 0.5 g and vanadium oxysulfate (VOSO ₄ xH ₂
O) 1.0 g was dissolved in DMF 200 ml and the solution was refluxed for 43 hours (153 ° C.). Then, the solvent was distilled off to obtain a crude product, which was dissolved in 60 ml of chloroform and washed with water three times,
Chloroform was distilled off to obtain Poly AOTPPVO (II). This was purified by repeating the operation of dissolution-precipitation using a mixed solvent of chloroform-methanol to obtain purified Poly AOTPPVO (II) with a yield of 92%. VO (II) of this product was obtained. The VO (II) content of this product was 50 mol%.

Poly AOTPPVO (II) whose VO (II) content is 50 mol%
And the Pol obtained in Example 1 with a VO (II) content of 100 mol%
Figure 3 shows the relationship between the temperature and magnetic susceptibility of y AOTPPVO (II). As can be seen from this figure, Poly AOTPPVO (II) with a VO (II) content of 50 mol% exhibits paramagnetism, while Poly AOTPPVO (II) with a VO (II) content of 100 mol% exhibits antiferromagnetism. Show.

(Example 9) AOTPP was obtained in the same manner as in Example 7, 0.50 g of this AOTPP and 0.25 g of copper acetate were dissolved in 200 ml of chloroform and refluxed for 3 hours, and then unreacted copper acetate was removed by filtration. I removed it. After washing the filtrate three times with water, the solvent was distilled off to obtain a crude product, and AOTPPCu (II) was isolated by a silica gel column, and then the dissolution-precipitation operation was repeated using chloroform and methanol. , Purified. Yield 0.43 g (78% yield).

The results of infrared analysis and elemental analysis of this product are shown below.

IR (KBr): 1745cm ^-1 (νc = o), 1635cm ^-1 (νc =
c) Elemental analysis Next, this 5- (4-acryloyloxyphenyl)-
10,15,20-Triphenylporphinate copper (II) [AOTP
PCu (II)] was used to carry out polymerization in the same manner as in Example 1 to obtain Poly AOTPPCu (II) having a weight average molecular weight Mw of 40,000 in a yield of 60%. The elemental analysis results of this product are shown below.

Elemental analysis

[Brief description of drawings]

1 and 2 are graphs showing the relationship between temperature and magnetic susceptibility and magnetization moment in different examples of the polymeric metal complex of the present invention, and FIG. 3 shows the polymeric metal complex of the present invention. It is a graph which shows the relationship between temperature and magnetic susceptibility in another example.

Claims (5)

(57) [Claims] 1. A general formula (In the above general formula, R is a hydrogen atom or a methyl group, and PM is a metal-containing porphyrin residue or a metal-containing porphyrin derivative residue in which an organic compound residue having an atom capable of coordinating to a central metal is unsubstituted. And R ¹ is 2,3,7,8,1 on the pyrrole ring in the metal-containing porphyrin residue or the metal-containing porphyrin derivative residue.
An alkylene group bonded to at least one of the 2,13,17,18 positions, or a methine group in the metal-containing porphyrin residue or the metal-containing porphyrin derivative residue.
An unsubstituted or substituted aryl group bound to at least one of 5,10,15,20) and having a molecular weight of 5,000 to 100,0
Polymer metal complex characterized in that it is 00. 2. An ester is obtained by making an organic compound residue having an atom capable of coordinating to a central metal unsubstituted and reacting a metal-containing porphyrin having an ester-forming functional group or a derivative thereof with an acrylic acid compound. Characterized by comprising a first step of producing a polymerizable monomer that binds the metal-containing porphyrin or a derivative thereof via a group, and a second step of polymerizing the polymerizable monomer.
General formula (In the above general formula, R is a hydrogen atom or a methyl group, and PM is a metal-containing porphyrin residue or a metal-containing porphyrin derivative residue in which an organic compound residue having an atom capable of coordinating to a central metal is unsubstituted. And R ¹ is 2,3,7,8,12,13, on the pyrrole ring in the metal-containing porphyrin residue or the metal-containing porphyrin derivative residue.
An alkylene group bonded to at least one of the 17,18 positions,
Alternatively, 5,10,15 of the methine group in the metal-containing porphyrin residue or the metal-containing porphyrin derivative residue,
Which is an unsubstituted or substituted aryl group bonded to at least one of 20). 3. An organic compound residue having an atom capable of coordinating to a central metal is made unsubstituted and a porphyrin or a derivative thereof having an ester-forming functional group is reacted with an acrylic acid-based compound to form an ester group. After obtaining an acrylic acid derivative that binds the porphyrin or a derivative thereof via a porphyrin, a first step of producing a polymerizable monomer by introducing a metal into the porphyrin residue, and a second step of polymerizing the polymerizable monomer The general formula, characterized in that (In the above general formula, R is a hydrogen atom or a methyl group, and PM is a metal-containing porphyrin residue or a metal-containing porphyrin derivative residue in which an organic compound residue having an atom capable of coordinating to a central metal is unsubstituted. And R ¹ is 2,3,7,8,12,13, on the pyrrole ring in the metal-containing porphyrin residue or the metal-containing porphyrin derivative residue.
An alkylene group bonded to at least one of the 17,18 positions,
Alternatively, 5,10,15 of the methine group in the metal-containing porphyrin residue or the metal-containing porphyrin derivative residue,
Which is an aryl group having an unsubstituted or substituted group in at least one of 20). 4. A polymer metal in which a metal-containing porphyrin and / or its derivative in which an organic compound residue having an atom capable of coordinating to a central metal is unsubstituted is introduced into a polymer main chain through an ester group. A polymer magnetic material comprising a complex. 5. A polymer complex having a general formula in the molecule (In the above general formula, R is a hydrogen atom or a methyl group, and PM is a metal-containing porphyrin residue or a metal-containing porphyrin derivative residue in which an organic compound residue having an atom capable of coordinating to a central metal is unsubstituted. And R ¹ is 2,3,7,8,12,13, on the pyrrole ring in the metal-containing porphyrin residue or the metal-containing porphyrin derivative residue.
An alkylene group bonded to at least one of the 17,18 positions,
Alternatively, 5,10,15 of the methine group in the metal-containing porphyrin residue or the metal-containing porphyrin derivative residue,
The polymer magnetic material according to claim 4, which has a repeating unit represented by the formula: (an unsubstituted or substituted aryl group bonded to at least one of 20).