JPH02160731A - Ferromagnetic organic substance having triarylmethane structure and production thereof - Google Patents

Abstract

NEW MATERIAL:A ferromagnetic organic substance having a triarylmethane structure consisting of a triarylmethane principal structure expressed by formula I [R<1> is >=2- cyclic substituted or unsubstituted condensed polycyclic arylene (which may contain hetero atom selected from N, S and O in the ring) or phenylene having electron donative substituent; R<2> is substituted or unsubstituted aryl; n is integer of >=3] wherein the radical concentration on the methine carbon site is >=10<17>/g. EXAMPLE:A condensed compound having a triarylmethane structure of formula 11. USE:An easily synthesizable stable ferromagnetic organic substance exhibiting ferromagnetism in high reproducibility and useful as a molecular element for magnetic recording material, photoelectric optical material, etc. PREPARATION:A precondensate of a ferromagnetic organic substance having ferromagnetic triarylmethane structure and a softening point of 30-120 deg.C and soluble in various solvents can be produced by condensing a >=2-cyclic substituted or unsubstituted condensed polycyclic aromatic compound, etc., with a substituted or unsubstituted aldehyde in the presence or an acid catalyst in a DC magnetic field.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a ferromagnetic organic polymer, particularly a precursor thereof, which is expected to find wide application in the field of molecular devices such as magnetic recording materials and optoelectronic optical materials. The present invention relates to a thermosetting initial condensate having a triarylmethane structure, a stable ferromagnetic organic substance derived therefrom, and a method for producing the same.

(Prior art) Conventionally known ferromagnetic organic substances include (1) kors
A black powdery polymer (Na
true.

326 370 (1987)), (2) Transformer (
Torrance)'s 1.3° 5-triaminobenzene is polymerized with iodine. -(Sy
nthoMetal, 19.709 (1987))
, (3) Hide Iwamura et al.'s polycarbenes (Journal of the Chemical Society of Japan, 1
987. Na4.595) etc. All of these are difficult to synthesize, leaving problems with reproducibility, only a few percent of the part exhibits ferromagnetism, the temperature at which magnetism occurs is extremely low, and they are unstable in air. There are problems such as.

Theoretical studies on the development of ferromagnetism are beginning to gain momentum, but the necessary and sufficient conditions for making organic materials develop ferromagnetism have not yet been determined, partly because sufficient ferromagnetic organic materials have not yet been synthesized. Not yet.

(Problem to be Solved by the Invention) The present inventors first disclosed a condensed polycyclic polynuclear aromatic (COPNA) resin produced from a condensed polycyclic aromatic compound using p-xylylene glycol as a linking agent in JP-A-62. It was proposed as No.-521 and No.62-522. This resin is characterized by excellent heat resistance, but subsequent research revealed that
By replacing the binder with benzaldehyde or benzenedialdehyde from p-xylylene glycol,
Furthermore, they succeeded in obtaining a thermosetting resin with high heat resistance, and proposed it as Japanese Patent Application No. 1982-282080. In the process of continuing this research, we accidentally confirmed that the resulting cured product or its precursor, a thermosetting initial condensate (B-stage resin), showed a slight reaction to permanent magnets. As a result of intensive research, the present invention was completed by solving all the problems associated with the conventionally known organic substances exhibiting magnetism.

An object of the present invention is to provide a thermosetting initial condensate corresponding to a stable organic polymer compound or its precursor that is easy to synthesize and exhibits ferromagnetism with good reproducibility.

(Means for Solving the Problems) That is, the organic polymer compound of the present invention for achieving the above object consists of a triarylmethane basic structure represented by the general formula, and has a radical concentration of at least 1 at the methine carbon site.
018/g, preferably R2 in the above formula is a substituted or unsubstituted phenyl group, more preferably n in the above formula is 10 or more, and the radical concentration at the methine carbon site is at least I Q I
fl/g.

Further, among the above-mentioned ferromagnetic organic substances having a triarylmethane structure, those with n less than 10 are 30"C to 12"
It is an initial condensate that has a softening point of 0°C and is soluble in various organic solvents and is defined as a stage resin. monocyclic aromatics, such as hydroxybenzene, and substituted or unsubstituted aromatics with electron-donating groups such as hydroxyl groups, lower alkyl groups, such as methyl groups, ethyl groups, lower alkoxy groups, such as methoxy groups, ethoxy groups, etc. In particular, the method of the present invention for obtaining a ferromagnetic organic material having a triarylmethane structure through such a B-stage resin is characterized by condensing an aldehyde with an aldehyde in a direct current magnetic field in the presence of an acid catalyst. The above substituted or unsubstituted condensed polycyclic aromatic compound or hydroxybenzene or electron donating group derivative of benzene is condensed with a substituted or unsubstituted aromatic aldehyde in the presence of an acid catalyst and softened at 30°C to 120°C. It is characterized by producing an initial condensate having a triarylmethane structure which has a triarylmethane structure and is soluble in various solvents, which is subjected to dehydrogenation treatment and removal treatment of unreacted substances, and then molded. Preferably, at least one of the condensation reaction of the initial condensate having a triarylmethane structure and the shaping is performed in a DC magnetic field.

Hereinafter, the present invention will be explained in further detail along with its functions.

As detailed in the aforementioned patent application, by heating an aromatic aldehyde with a condensed polycyclic aromatic compound such as anthracene or pyrene to a temperature of 140°C to 200°C in the presence of an acid catalyst, a softening point of 30°C can be obtained. A B-stage resin having a temperature of about 120°C can be obtained. A cured product can be obtained by continuing to heat this at the reaction temperature for a long time or by treating it for a short time at a temperature of 200°C to 300°C. If the aromatic group to be linked is replaced by a hydroxy derivative, such as phenol, resorcinol, monohydroxynaphthalene, or dihydroxynaphthalene, the reaction proceeds at even lower temperatures if the binder is benzaldehyde, which is liquid at room temperature.

In these reactions, the final cured product passes through the B-stage resin stage to which various molding methods can be applied.
This will be very advantageous when considering applications.

That is, a solution of the B-stage resin can be used to make a film by the casting method, or a melt can be used to make fibers and other molded products.

The following method was used as the simplest method for determining the magnetism of B-stage resins and cured products. Fill a glass petri dish with a diameter of 10 cm with water to a depth of 1 to 2 mm, and sprinkle the B-stage resin or cured product powder on top of it. The powder floats on the water surface. When a permanent magnet is left under this petri dish, the sample powder on the water surface gathers at the edge of the permanent magnet, where the magnetic flux density is strongest, and forms a line along the edge. The time required for the resin to gather at the edge of the magnet varies depending on the raw material and manufacturing conditions of the resin. Fastest one is within 30 seconds, slow one is 1
We will gather around 0 minutes. Of course, there are times when they don't come together at all. After these preliminary magnetic comparisons, the magnetic properties of the main samples were measured using a vibrating sample automatic magnetization characteristic recorder (νSM) manufactured by Riken Denshi Co., Ltd.

As a result of initial studies, it was confirmed that proceeding with the condensation reaction in a magnetic field or further proceeding with the reaction in a magnetic field using a B-stage resin prepared in advance with a low softening point is effective for developing ferromagnetism. did. Specifically, you can place a reaction vessel in the center of the coil while passing direct current through it, or you can place the reaction vessel between the poles of a large electromagnet.The simplest method is to place a glass plate or aluminum plate on top of a permanent magnet. A foil or release paper is placed, the initial B-stage resin solution is placed thereon, the solvent is removed, and if necessary, the resin is heated to proceed with condensation and then peeled off. Alternatively, it can be heated by sandwiching it between upper and lower magnets.

Although it was confirmed that a polymer exhibiting ferromagnetism at room temperature could be obtained by this method, the problem was that some parts showed ferromagnetism and others did not, and the yield of the ferromagnetic part was low. Although the reason for this has not yet been academically elucidated, we assumed two possibilities and considered adding a new processing method.

Analysis of the molecules constituting the B-stage resin, mainly by nuclear magnetic resonance absorption, revealed that these molecules have a triarylmethane type structure.

Based on this, we assumed the following two possibilities for improving the yield of the ferromagnetic part.

One is to increase the radical concentration by removing the hydrogen bonded to the methine carbon at the center of the triarylmethane structure, and the other is to increase the radical concentration by removing the hydrogen bonded to the methine carbon at the center of the triarylmethane structure. It is to remove molecules.

Both of these two attempts were effective in improving the properties and yield, and as a result, it was found that the process with the suitable amount was as shown in the process flow sheet shown in FIG. 1 of the attached drawings.

Of these steps, the order of dehydrogenation treatment and separation operation may be interchanged. The key is that these two operations are included.

These manufacturing methods will be explained in more detail below.

The fused polycyclic aromatic compounds applicable to the method of the present invention include those having about 2 to 10 rings, such as naphthalene, anthracene, phenanthrene, pyrene, chrysene,
In addition to benzene ring condensed types such as naphthacene, benzophenanthrene, perylene, benzopyrene, coronene, etc., acenaphthylene, decacyclene, etc. may contain a 5-membered ring, and may also contain a heteroatom such as N, S, or O as a ring member. But that's fine. Furthermore, substituted derivatives such as hydroxyl group and methyl group can also be suitably applied. These may be a mixture.

In the case of monocyclic aromatics, the reaction is difficult to proceed with unsubstituted benzene; Substituted substances such as phenol and resorcinol can also be used as typical examples.

Among the above-mentioned fused polycyclic aromatic compounds, pyrene has particularly high reactivity and is easy to produce. Even in the case of naphthalene, hydroxy derivatives are highly reactive, and the reaction proceeds at lower temperatures and in a shorter time than with pyrene. For example, various dihydroxy derivatives of naphthol or naphthalene. In the case of derivatives substituted with hydroxyl groups or other electron-donating groups, including monocyclic aromatic compounds, the reactivity of the ortho and rose positions of the substituents is particularly high, so the reaction position with the linking agent can be determined, and the structure Another advantage is that it is easy to control. If this is shown for the reactions between phenol and benzaldehyde and between resorcinol and benzaldehyde, the following equations (2) 2 and (3) are obtained, respectively.

The linking agent is characterized by being an aromatic aldehyde or a substituted derivative thereof. Examples of the substituent include a nitro group, hydrogen, methyl group, isopropyl group, L-butyl group, hydroxyl group, and amino group. Among such aromatic aldehydes, benzaldehyde or its methyl or nitro derivatives are most commonly used. In many cases, resin moldability is better when benzenedialdehyde, a disubstituted derivative, is used.

The molar ratio of linking agent to aromatic is often 1 or more, as seen in the examples. The final product in this case is a three-dimensional triaryl structure.

As the catalyst, various acid catalysts such as various aromatic sulfonic acids including p-toluenesulfonic acid, fluoromethanesulfonic acid and other super strong acids, sulfuric acid, etc. can be used.

The reaction between an aromatic aldehyde and an aromatic compound when an acid catalyst is used is, for example, the reaction between pyrene and benzaldehyde (4
) Proceed with the formula. This can also be confirmed by structural analysis of the product.

In other words, the compound obtained by such a reaction is "
A resonance absorption spectrum appears at a position around 50 ppm in the CNMR spectrum, clearly indicating the presence of a carbon atom forming a methine bond. The exact position of the spectrum varies slightly depending on the raw materials used. For example, the concentration is 54 ppm for pyrene/benzaldehyde systems, and 47 ppm and 53 ppm for phenol/benzaldehyde systems. From this, the structural characteristics of the condensate, which is the reaction product, are as follows:
The triarylmethane structure is used as a unit, and -a
As a general name, it should be called a condensate having a triarylmethane structure. The basic reaction is the same for aromatic dialdehydes, such as terephthalaldehyde, and the result is a three-dimensional macromolecule with a triarylmethane structure as a unit.

The basic repeating structural unit of the condensate having such a triarylmethane structure can be represented by the following formula (1).

Subsequent research has shown that when using compounds that have an electron-donating group such as a hydroxy group, a lower alkyl group, such as a methyl group, an ethyl group, a lower alkoxy group, such as a methoxy group, or an ethoxy group, and an aldehyde group in the same aromatic nucleus, It was found that a triarylmethane polymer compound having the basic structure of the following formula (5) can be obtained by heating only the compound in the presence of an acid catalyst.

ν In the formula, " is a substituted or unsubstituted fused polycyclic arylene group having two or more rings (however, the ring member may contain a heteroatom consisting of N, S or O) or a hydroxyphenyleso group, and R8 is a substituted or Represents an unsubstituted aryl group, n is 3
is an integer greater than or equal to

The structure of this reaction and the resulting product is illustrated with p-hydroxybenzaldehyde. The hydroxy group is an ortho- and para-directing group, but since the para position has already been substituted with an aldehyde group, substitution is selectively carried out at the ortho position. The essence of the reaction is the same as in the case of a mixture of phenol and benzaldehyde, and proceeds as shown in the following formula (6).

H However, since the hydroxy group and the aldehyde group are present in the same aromatic nucleus, the unit structure of the resulting triarylmethane type polymer changes, and the higher-order structure changes accordingly. The details of this higher-order network structure have not yet been confirmed, but the basic structure that is the unit is
Confirmed from CNMR results and reaction analysis. The basic factor for magnetic expression is this unit structure.

The aromatic nucleus having two types of substituents may be a monocyclic ring such as hydroxybenzaldehyde or a condensed polycyclic ring such as naphthalene. However, if the goal is to increase the radical concentration per unit weight, the monocyclic ring is most advantageous.

The radical concentration calculated from paramagnetic resonance absorption measurements of the product produced under conventional methods and conditions is 1016 to 101'l per gram, which is not necessarily high. Even in this case, the radical concentration of the product when heated and condensed in a magnetic field increases to 1011 to 10111/g, and in the preliminary test method described above, it sometimes collects on the edge of the magnet within 30 seconds. In addition, a vibrating sample-type magnetization characteristic automatic recording device (V
According to SM), it exhibits magnetic anisotropy, and in the direction perpendicular to the film plane, which corresponds to the direction parallel to the magnetic field, the saturation magnetization is 5.
．． 64 gauss and coercive force of 100 oersteds, and those of 5.84 gauss and 160 oersteds in the direction parallel to the magnetic field were also observed. However, the yield of samples exhibiting such high magnetic properties is small, often not exceeding a few percent.

We confirmed that several methods are effective for dehydrogenation treatment to remove hydrogen attached to methine carbon and increase radical concentration. One method is to make a B-stage resin using a benzaldehyde/pyrene (molar ratio 1.25) mixture as raw material, pulverize it, suspend it in dry xylene with an equimolar amount of dicyanodichlorobenzoquinone (DDQ), and then This is a method in which the mixture is heated at boiling temperature for 24 hours and then filtered. When DDQ and unreacted raw materials are extracted and removed from the sample obtained by this method using tetrahydrofuran (THF), a sample clearly exhibiting ferromagnetism can be obtained, although the yield is as low as 1 to 3%.

The following method is also effective as a dehydrogenation method with higher yield. The B-stage resin was made into a chloroform solution, equimolar benzoquinone (BQ) was added as a photosensitizer, and the solution was heated at 370° C. using a high-pressure mercury lamp.
This is a method of irradiating nanometer ultraviolet rays for one hour or more. In this method, after the treatment, the solution is poured into methyl alcohol to precipitate only the reaction product, and about 70 to 85%
Ferromagnetic organic materials can be obtained in high yields. This product still has a softening point of around 80°C and can be subjected to various molding methods and can be further condensed.

Another interesting dehydrogenation treatment method was also confirmed.

This involves discharging using a capacitor with B-stage resin in between. Magnetism is clearly enhanced in this way as well. This method has the potential to become an extremely important means of locally imparting magnetism to film-like samples in the future.

In short, this dehydrogenation treatment does not have to be particularly limited in its method, and all commonly used methods are effective. It is possible to use a sensitizer, and the effect can be further enhanced by ultraviolet irradiation, laser irradiation, or electrical treatment using discharge.

Through this dehydrogenation treatment, the radical concentration is reduced to 101
It increases to about 8 to 1018/g.

Although it has been possible to improve the yield of magnetic organic materials by combining dehydrogenation treatment and separation of unreacted substances, an effective molding method is required when considering the use of this material. Fortunately, B-stage processed materials often soften, melt, or dissolve in a solvent. Therefore, it can be molded by a hot press molding method or a casting method, and the curing reaction progresses when heating is continued. Utilizing this property, it can be molded into various shapes. In this case, carrying out this molding process in a DC magnetic field leads to further improvement in magnetism, which is the same as already stated for the sample that is not subjected to dehydrogenation treatment. However, by using a dehydrogenated B-stage resin, the magnetism and yield of the molded sample are significantly improved compared to when a non-dehydrogenated sample is used.

Although it is possible to make various molded products in this way, the ease of molding is recognized to be difficult depending on the combination of the aromatic compound and the linking agent. For example, to make a film-like sample, the most suitable combination is a disubstituted electron-donating group such as benzene or naphthalene as an aromatic compound, such as a hashihydroxy derivative, and benzaldehyde as a linking agent. The most suitable combination is pyrene and benzenedialdehyde. Further, in order to make a fibrous molded product, a B-stage resin which is an initial condensation product is desirable.

In order to further improve the moldability, it is also effective to add p-xylylene glycol or its methyl derivative in an appropriate proportion to the B-stage resin.

The color of the product varies depending on the type of raw material composition and the stage of progress of the reaction. When benzaldehyde is combined with an electron-donating disubstituted product such as a dihydroxy derivative of benzene or naphthalene, the color changes from a pale red color to a deep color as the reaction progresses.

When pyrene is combined with benzaldehyde or terephthalaldehyde, the color changes from yellowish-green to deeper and finally becomes black.

At the B-stage resin stage, the resin generally exhibits an average molecular weight of about 4 aromatic nuclei linked together, and unreacted aldehyde groups remain. However, in the cured product obtained at 200° C. or higher, no aldehyde groups are observed and only methine bonds are present. Magnetism is developed at any stage.

The mechanism of magnetic expression has not yet been elucidated. However, what can be clearly pointed out at this stage is that (1) polymer compounds with a specific triallylmethane structure as a unit exhibit ferromagnetism, and (2) polymers with such a structure are A ring aromatic compound or an electron-donating group substituted product of benzene, such as the reaction of hydroxybenzene with an aromatic aldehyde, or the self-polymerization of a compound having an electron-donating group and an aldehyde group in the same aromatic nucleus, (
3) dehydrogenation treatment and separation and removal of unreacted substances improve properties and yield; and (4) molding and reaction operations in a magnetic field promote the development of magnetism.

Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not intended to be limited by these Examples.

Example 1 5% by weight of para-toluenesulfonic acid (PTS) was added to a mixture of benzaldehyde and pyrene at a molar ratio of 1.25, mixed well, and stirred in an argon stream until 1.
The reaction was carried out at 60°C for 60 minutes to obtain a stage resin which had a softening point of about 80°C and was soluble in various solvents.

A small piece of this resin is sandwiched between aluminum foil, and two permanent magnets (H18B manufactured by Hitachi Metals, Ltd.) are placed one above the other.
The temperature was raised to 160°C at a rate of 5°C/min, and the temperature was about 0.
A film-like sample of about 7n+m was obtained.

The sample broke into small pieces of several square millimeters during peeling, but
There is a small piece that shows magnetism in it, and the V
A magnetization curve showing hysteresis as shown in FIG. 2 was obtained by SM. The saturation magnetization determined from this result is 5.64 Gauss (G) in the direction perpendicular to the film plane and 5.84 G in the parallel direction, and the coercive force is 100 Oe and 160 Oe, respectively. Met. However, the yield of small pieces exhibiting ferromagnetism was only a few percent.

Example 2 5% PTS was added to a mixture of terephthalaldehyde/pyrene (molar ratio 1, 25) and heated to 160 ml under a stream of argon.
A B-stage resin was prepared by heating at ℃ for 1 hour.

Next, an electromagnet (Japan Electron 0pt
A DC magnetic field of 1.57 (Tesler) was created using a ICS LaboratoryCo, Ltd. JM-393 model), and a non-inductive heating coil was placed in it with a diameter of 1 cm.
Place a heating device wrapped around a glass tube, and insert a glass port containing B-stage resin into it. A dark green molded product was obtained by heating at 160° C. for a period of time in an argon stream. The radical concentration by ESR is l Q l [1/g
Met. The saturation magnetization of this material was 0.110e, and the coercive force could not be accurately determined.

Example 3 5% PTS was added to a mixture of benzaldehyde/pyrene (molar ratio 1.25) for 160' under a stream of argon.
A B-stage resin was obtained by heating for 190 minutes.

Spread this resin powder 3 times in advance to a depth of 2 mm.
% hydrogen peroxide in a petri dish. When two copper wires are placed 1 to 2 mm apart and a voltage of 500V is applied using a constant voltage DC power supply, the resin powder gathers between the poles in order from the one closest to the pole, and a discharge occurs there. At the same time, the powder rapidly moves away while floating on the water surface. After successive treatments in this manner, the powder is filtered, washed with water, and then dried.

The obtained powder was placed in a Petri dish (10 cm in diameter).
When the powder was sprinkled on the water surface at a depth of about mm and a magnet was placed under a petri dish, the powder gathered around the edge of the magnet.

Example 4 5% by weight of PTS was added to a mixture of benzaldehyde and pyrene at a molar ratio of 1.25, mixed well, and reacted at 160°C in an argon stream for 60 minutes to obtain a B-stage resin with a softening point of 8°C. Obtained 5 grams. This was dissolved in 25 d of chloroform, about 1.5 g of benzoquinone was added, and the mixture was irradiated with a high-pressure mercury lamp for 12 hours. This solution is about 5Or#1
The mixture was poured into methanol and the precipitate was filtered off. The resulting precipitate was white and the yield was about 80%. The radical concentration by ESR is 1019-1020/g, and magnetic measurement with VSM shows that the saturation magnetization is 0.11 G and the coercive force is 6.
It was 40e.

Example 5 Electromagnet (Japan Electron 0ptics)
Manufactured by LaboratoryCo, Ltd. J? l-39
3 type) to create a DC magnetic field of 1.57 (Tesler), and a non-inductive heating coil with a diameter of 1 cm (inner diameter) in it.
A heating device wrapped around a glass tube was placed, and 0.8 g of the white method # obtained in Example 4 was placed in a glass boat and placed in the heating section, and heated at a rate of 5°C/min in an argon stream. The temperature was raised to 160°C and held for 2 hours. Then again 5
The temperature was raised to 250° C. at a rate of 1°C/min. Meanwhile, 10
It was held for 10 minutes at each temperature in the 'C interval. The obtained sample was a dark green solid with a radical concentration of 10 '' /
It was g.

Scatter small pieces of this sample on the surface of water at a depth of about 1 mm in a petri dish (10 cm in diameter), and place a magnet (
H18B) was placed, and after a while it gathered around the edge of the magnet. - Once they started to gather around the edges, even if I shook the water and scattered the pieces, they immediately gathered around the edges. According to the magnetic measurement of this sample, the saturation magnetization is 5.0G and the coercive force is 2000
It was e.

Example 6 Benzaldehyde in a 1.25-fold molar amount and PTS corresponding to 5% by weight of their total weight were added to carbazole and thoroughly mixed. Then, it was transferred to a test tube and heated at 160° C. for 5 to 10 minutes in an argon stream to obtain a B-stage resin.

3g of this B-stage resin in 20d of dichloromethane? This was poured into 60 ml of methanol.

Since only the reaction product precipitated, it was filtered to separate and remove the acid catalyst and unreacted substances.

The obtained resin was placed in a test tube, and benzoquinone (BQ
) was added. Next, add about 1 liter of dichloromethane to the test tube.
After adding 0ml to completely dissolve the mixture, it was stirred uniformly using ultrasonic waves. This was irradiated with light for 24 hours at room temperature using a high pressure mercury lamp with an output of 450.

The sample solution after irradiation was poured into methanol to precipitate the resin. After the precipitate was filtered off, it was transferred to a Soxhlet extractor, and the resin was washed using methanol as a solvent for 10 hours.

A few mg of small pieces of the purified resin were placed in a petri dish (10 cm in diameter).
), and when a permanent magnet (H18B) was placed under the petri dish, the particles gathered at the edge of the magnet where the density of magnetic lines of force was highest.

- Once they started to gather around the edges, even if I shook the water and scattered the pieces, they immediately gathered around the edges.

Example 7 1.6-hydroxynaphthalene and 1.25 times the molar amount of benzaldehyde were mixed, 3% by weight of PTS was added thereto, and the mixture was heated while stirring in a nitrogen stream. first 5
After being held at 0°C for 1 hour, the temperature was raised to 100°C for 1 hour, and then heated at 130'C for 2 hours.

The product was obtained, which was still a highly viscous liquid at the reaction temperature, but a dark red solid at room temperature.

After pulverizing the solid product, benzoquinone is mixed in an amount of 1.5 times the molar amount relative to the structural unit, the mixture is placed in a quartz test tube, and about 20 d of dichloromethane is added. Benzoquinone dissolves, but resin powder does! AA pre-turbidity state.

This was irradiated with light for 12 hours while stirring at room temperature using a 450 W high pressure mercury lamp. The sample solution after irradiation was poured into a large excess of dichloromethane, and the precipitate was filtered off.

When these small pieces were scattered on the surface of water at a depth of about 1 mm in a petri dish and a magnet was placed under the dish, the pieces gathered around the edge of the magnet.

Example 8 1% by weight of PTS was added to a mixture of benzaldehyde and phenol at a molar ratio of 1.25, mixed well, and reacted at 130° C. for 60 minutes to obtain a red B-stage resin. After crushing this resin, 1 gram of it and about 0.0 gram of benzoquinone are combined.
5 grams were dispersed in about 20 mfl of cyclohexane and irradiated with a high pressure mercury lamp for 12 hours. After irradiation, the solution was poured into about 200 ml of cyclohexane and the precipitate was filtered off to obtain a red product. The yield was about 70-80%. According to the results of magnetic measurement by VSM, this resin had a saturation magnetization of 0.2 G and a coercive force of 9008.

Example 9 Add 1% by weight of PTS to hydroxybenzaldehyde, mix well, and react at 130°C for 20 minutes to produce red B.
A stage resin was obtained. After pulverizing this resin, 1 gram of it and about 0.5 gram of benzoquinone were dispersed in about 20 ml of cyclohexane and irradiated with a high pressure mercury lamp for 12 hours. After irradiation, the solution was poured into about 200 Id of cyclohexane and the precipitate was filtered off to give a red product.

The yield was about 70-80%. According to the results of magnetic measurement by VSM, this resin had a saturation magnetization of 0.5 G and a coercive force of 100 e.

〔Effect of the invention〕

As mentioned above, by providing ferromagnetic polymers that exist stably in the air, can be synthesized with good reproducibility, and can be formed into films, fibers, and various other shapes, magnetic recording materials, optoelectronic optical materials, etc. It has now become possible to develop a new field as a molecular device.

[Brief explanation of the drawing]

FIG. 1 is a process flow sheet of the method of the present invention, and FIG. 2 is a graph showing the magnetization curve of the polymer of the present invention.

Claims (1)

[Claims] 1. General formula▲ Numerical formulas, chemical formulas, tables, etc.▼...(1) [In the above formula, R^1 is a substituted or unsubstituted fused polycyclic arylene group of two or more rings (provided that , a ring member may contain a heteroatom consisting of N, S or O) or an electron-donating group-substituted phenylene group, R^2 represents a substituted or unsubstituted aryl group, and n is an integer of 3 or more] The radical concentration at the methine carbon site is at least 1
A ferromagnetic organic material having a triarylmethane structure, characterized in that the magnetic flux is 0^1^7/g. 2. The ferromagnetic organic material having a triarylmethane structure according to claim 1, wherein R^2 in the general formula is a substituted or unsubstituted phenyl group. 3. n in the general formula is 10 or more, and the radical concentration at the methine carbon site is at least 10^1^8/
3. The ferromagnetic organic polymeric substance having a triarylmethane structure according to claim 1 or 2, wherein the ferromagnetic organic polymer substance has a triarylmethane structure. 4. A substituted or unsubstituted condensed polycyclic aromatic compound having two or more rings or an electron donating group-substituted benzene is condensed with a substituted or unsubstituted aromatic aldehyde in the presence of an acid catalyst in a direct current magnetic field 30 A method for producing an initial condensate of a ferromagnetic organic substance having a ferromagnetic triarylmethane structure having a softening point of 120°C to 120°C and soluble in various solvents. 5. A substituted or unsubstituted condensed polycyclic aromatic compound having two or more rings or an electron donating group-substituted benzene is condensed with a substituted or unsubstituted aromatic aldehyde in the presence of an acid catalyst, and the mixture is heated at 30°C.
An initial condensate having a triarylmethane structure having a softening point of 120°C to 120°C and being soluble in various solvents is produced, and after being subjected to dehydrogenation treatment and removal treatment of unreacted substances, it is molded. A method for producing a ferromagnetic organic polymer substance having a characteristic triarylmethane structure. 6. The ferromagnetic organic polymer material having a triarylmethane structure according to claim 5, wherein at least one of the condensation reaction of the initial condensate having the triarylmethane structure and the shaping is performed in a DC magnetic field. manufacturing method. 7. The molding is carried out in a magnetic field of at least 100 Gauss, and (1) a step of evaporating the solvent of the solution of the initial condensate having a triarylmethane structure; (2) a step of melting the initial condensate having a triarylmethane structure; , (3) After the above step (1) or (2), the condensation reaction is proceeded by one of the following steps of heating to a temperature of 120 ° C. or higher to form a cured product that is insoluble in a solvent and does not melt. The manufacturing method according to claim 6. 8. The method of claim 7, wherein the magnetic field strength is at least 400 Gauss. 9. As the dehydrogenation treatment, at least one photosensitizer selected from the group consisting of benzoquinone, benzophenone, dicyanodichlorobenzoquinone, and azobisisobutyronitrile is added to the solution of the initial condensate having a triarylmethane structure. 6. The manufacturing method according to claim 5, further comprising heating or irradiating with ultraviolet rays. 10. The manufacturing method according to claim 5, wherein the dehydrogenation treatment uses electric discharge. 11. The manufacturing method according to any one of claims 4 to 10, characterized in that benzaldehyde, benzenedialdehyde, or a derivative thereof is used as the aromatic aldehyde. 12. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼...(5) [In the above formula, R^3 represents a substituted or unsubstituted aromatic nucleus, and n
is an integer of 3 or more], and the radical concentration at the methine carbon site is at least 10
A ferromagnetic organic material having a triarylmethane structure, characterized in that it has a triarylmethane structure of ^1^7/g. 13. In the ferromagnetic organic substance having a triarylmethane structure according to claim 12, R^3 is an electron donating group-substituted aromatic nucleus, n is 10 or more, and the radical concentration at the methine site is at least 10^. 1^8/g ferromagnetic organic polymer material. 14. Reacting an aromatic derivative having at least one electron donating group and at least one aldehyde group by heating in the presence of an acid catalyst, followed by dehydrogenation by light irradiation or the use of an oxidizing agent. General formulas characterized by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (5) [In the above formula, R^3 represents an electron-donating group-substituted aromatic nucleus, and n is an integer of 10 or more] The radical concentration at the methine site is at least 10^
A method for producing a ferromagnetic organic polymer material having a magnetic flux of 1^8/g. 15. The aromatic derivative is para- or meta-hydroxybenzaldehyde, and the light irradiation is carried out in the presence of at least one oxidizing agent selected from the group consisting of benzoquinone, benzophenone, dicyanodichlorobenzoquinone, and azobisisobutyronitrile. 15. The method for producing a ferromagnetic organic polymer material according to claim 14.