JPH0196217A - Novel polymer complex and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled ferromagnetic complex with the hydrolysis suppressed even in an aqueous solution of the transition metal salt for complex formation, by reaction of a specific polycondensate with said aqueous solution at temperatures below a specified level. CONSTITUTION:The objective complex can be obtained by reaction of (A) a polycondensate constituted of recurring unit of formula (n is 2-12), with a specific viscosity etasp/c (in the form of chloroform solution containing 0.2mol. of m-cresol) of 0.2-1.5 with (B) an aqueous solution of transition metal salt (e.g. ferrous sulfate) pref. at room temperature.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a novel polymer complex and a method for producing the same.

More specifically, the present invention relates to a polymer complex exhibiting ferromagnetism and a method for producing the same.

[Conventional technology]

At present, α,ω-diaminoalkanes and 2,
A polycondensate with 6-pyridinedicarboxaldehyde having a repeating unit represented by the following general formula is known (J.

Am, Chew, Soc, Vol. 79, p. 2738,
1957).

However, in order to make this polycondensate into a complex with ferrous sulfate and retain its magnetism, it must be boiled in an aqueous solution of ferrous sulfate, but the polycondensate itself is resistant to hydrolysis. Complexation under such conditions is never desirable because of the poor

In other words, this polycondensate has the property of being easily hydrolyzed at the azomethine moiety (-CH=N-) in the main chain in an acidic atmosphere, and therefore cannot be easily hydrolyzed in an acidic ferrous sulfate aqueous solution. It undergoes hydrolysis, and after being immersed in a boiling aqueous solution for about 10 minutes, it decomposes to the point that it cannot be recovered using a membrane filter with a pore size of 0.2 μm. On the other hand, in order to avoid such a situation, if iron ions are coordinated under room temperature conditions, a complex is formed there, but the resulting polymer complex does not have ferromagnetism.

[Problem that the invention seeks to solve]

As a result of various studies in search of a polymer complex that exhibits ferromagnetism even at room temperature, the present inventors discovered a polymer complex in which the hydrogen atom of the -CH=N- bond in the general formula [U] was converted into a methyl group. It has been found that a condensate can effectively solve the above problems.

[Means for solving problems]

Therefore, the present invention relates to a novel polymer complex, which has a repeating unit represented by the general formula and has a specific viscosity ηSP/c (
0.2 mol m-cresol in chloroform solution, 30
C) of about 0.2 to 1.5.

The present invention also relates to a method for producing such a novel polymer complex,
The polymer complex is produced by reacting the polycondensate with an aqueous transition metal salt solution at a temperature of about 40° C. or lower.

The polycondensate used here has the general formula Hz N (CH2)nNHz (where n=2 to 1
α,ω-diaminoalkane represented by 2) and 2,
It is produced by polycondensation reaction with 6-diacetylpyridine.

Generally, 1,6-diamithexane is used α, ω
- The polycondensation reaction between diaminoalkane and 2,6-diacetylpyridine is carried out using alcohols such as methanol and ethanol, and chlorinated hydrocarbons such as chloroform and 1,1,2,2-tetrachloroethane. be exposed.

In the case of an alcohol solvent, a polycondensate with a relatively low degree of polymerization (the degree of polymerization is thought to be about 5 to 10) is obtained, and chlorinated hydrocarbons that dissolve both the monomer and the polymer are used as the solvent.

When O-lm- or P-cresol as a catalyst is added thereto at a concentration of about 0.1 to 3 molar.

A product with a higher degree of polymerization capable of forming a film-like material can be obtained. Polycondensation reactions using such solvents are conducted at temperatures from room temperature to about 60°C.

The presence of -C(CH3)=N- bonds in the main chain of the obtained polycondensate was confirmed from the infrared absorption spectrum, and its specific viscosity was ηsp/c (0.2 mol m-cresol in chloroform solution, 30° C.) is within a value range of approximately 0.2 to 1.5.

Coordination of transition metal ions to polycondensates can be achieved, for example, by
Iron heptahydrate, cobalt (n) sulfate heptahydrate.

Ferric perchlorate, hexahydrate, etc., in pure water at a concentration of about 0.1 to 1
This is carried out by immersion in an aqueous solution dissolved at a concentration of 0% by weight at a temperature below about 40°C, preferably between about 40°C and 10°C, generally at room temperature. The dipping operation is carried out by first leaving it in a nitrogen atmosphere for about 2 to 10 hours, then in air for about 2 to 10 hours, and then separating it for a day and drying it to obtain a polymer complex.

[Action] and [Effects of the Invention] - in the main chain of the polycondensate coordinating transition metal salt ions.
By substituting a methyl group on the CH=N- bond, the hydrolysis reaction can be suppressed even in a transition metal salt aqueous solution for complex formation due to its steric hindrance, and even without boiling in a transition metal salt aqueous solution, approximately A ferromagnetic polymer complex can be formed at 40° C. or lower, for example at room temperature.

Moreover, such a magnetic polymer complex can also be obtained in the form of a film or a fiber by using a polycondensate having a higher degree of polymerization.

〔Example〕

Next, the present invention will be explained with reference to examples.

Reference Example 1 To a reflux solution of 20 m Q of an ethanol solution of 1,6-diamithexane with a 1.3 molar concentration, 20 m Q of an ethanol solution of 2,6-diacetylpyridine with the same concentration was added dropwise in a nitrogen atmosphere, and about The reaction was allowed to proceed for 80 minutes, and the precipitated polycondensate was washed with ethanol every day.

When the infrared absorption spectrum of the resulting polycondensate was measured, as shown in the chart of Figure 1,
l630a+! -C(CH,)=N- in the main chain near 1
A stretching vibration peak of the group <-C=N- was observed in the bond.

Further, the specific viscosity ηsp/c of this produced polycondensed metal is 0.27
Met.

Reference Examples 2 to 4 In Reference Example 1, the ethanol solution concentration of each monomer was changed to 0.5, 1.0 or 1.5 mol, respectively.

All of the produced polycondensed metals showed infrared absorption spectra similar to the chart in Figure 1, and the specific viscosities ηSP/c were 0.25, 0.27, and 0.28, respectively. Reference Example 5 Reference Example In Example 1, the solvent for each 7-mer was changed to methanol. The infrared absorption spectrum and specific viscosity of the produced polycondensed metal were the same as those of Reference Example 1.

Reference example 6 In Reference Example 1, the reaction temperature was changed to room temperature.

The produced polycondensed metal showed an infrared absorption spectrum similar to that shown in the chart of FIG. 1, and had a specific viscosity ηSP/c of 0.26.

Reference Example 7 In Reference Example 1, a chloroform solution in which m-cresol as a catalyst was dissolved at a concentration of 0.2 molar was used instead of the solvent ethanol, and the reaction time was extended to about 24 hours. After the reaction was completed, the reaction mixture was poured into methanol to precipitate the produced polycondensate. This generated degenerate metal is
Specific viscosity ηSP/e was 0.50.

0.2 mol m- of the polycondensate used for this specific viscosity measurement
When we measured the change over time in the specific viscosity of a chloroform solution of cresol, we obtained the results shown by the solid line in the first diagram.

On the other hand, when we measured over time the dead activity of a chloroform solution of 0.2 mol of a polycondensate of 2,6-pyridinedicarboxaldehyde and 1,6-diamithexane, we found that Results as shown by the dotted line were obtained, that is, a rapid decrease in specific viscosity was observed up to about 30 minutes after solution preparation, and a tendency was observed for the specific viscosity to gradually decrease thereafter.

Reference Examples 8 to 9 In Reference Example 7, the concentration of the m-cresol chloroform solution was changed to 1.0 or 2.5 mol. The resulting polycondensed metal has a specific viscosity η sp/c of 1.21 and 1
．． It showed a value of 22. In addition, its infrared absorption vector is shown in the first diagram, and the peak derived from the C=O stretching vibration of the terminal −〇 (CH,) = 0 group seen in the chart in Figure 1 is also included in the chart. (1700am')
could not be detected, indicating that a polycondensate with a high degree of polymerization was produced. This polycondensate with a high degree of polymerization can form a film.

Reference Examples 10 to 11 When p-cresol or 0-cresol was used in place of 1m-cresol in Reference Example 7, the resulting polycondensates each had a specific viscosity ηsp/c of 0.52.

Reference Example 12 In Reference Example 7, 1,12-diaminododecane was used instead of 1,6-diamitsuhexane and was reacted with 2,6-diacetylpyridine.

The resulting polycondensate has stronger hydrophobicity than the polycondensate obtained in Reference Example 7, and its specific viscosity ηsp/c is 0.48.
Met.

Reference Comparative Example In Reference Example 1, m-cresol was used instead of the solvent ethanol, the reaction temperature was set to 60° C., and the reaction was carried out for 24 hours, but no polymer formation was observed.

Example 1 The polycondensate obtained in Reference Example 1 was added to an aqueous solution (concentration 1.1%) of 0.54 g of ferrous sulfate heptahydrate dissolved in 50 mm of pure water at room temperature under a nitrogen atmosphere. 0.50g was added.

Immediately after the addition, the solid polycondensate was colored purple.

After being left in a nitrogen atmosphere for 8 hours and then in the air for 7 hours, the resulting polymer complex was dried and measured for magnetization. As it showed a hysteresis curve, it was confirmed that it was a ferromagnetic material. .

Saturation magnetization Ms=2.6smu/g Residual magnetization Mr=0.5smu/g Coercive force Hc=800s On the other hand, 2,6-pyridinedicarboxaldehyde and 1.
Iron ions were coordinated to the polycondensate with 6-diamithexane in the same manner, but the resulting polymer complex did not exhibit ferromagnetism but was paramagnetic. In order to maintain magnetism in such a polymer complex, J, Am, Chew,
Sac, Vol. 79, p. 2738 (1957), 1.8 g of ferrous sulfate heptahydrate was added to 25 ml of pure water.
An aqueous solution (concentration 6.7 times the polycondensate 0.
It requires adding 65g and boiling.

On the other hand, in the present invention, the transition metal salt concentration is about 176, and the magnetism that is different from that of the conventional method can be developed without heat treatment.

Example 2 0.50 g of the polycondensate obtained in Reference Example 1 was added to an aqueous solution of 0.65 g of cobalt sulfate heptahydrate dissolved in pure water at room temperature in a nitrogen atmosphere. Immediately after the addition, the solid polycondensate gradually turned red. 8 hours in a nitrogen atmosphere
After being left in the air for 7 hours, it was dried for another day. The obtained polymer complex adhered to a magnet and exhibited ferromagnetism.

[Brief explanation of the drawing]

FIG. 1 and the second diagram are infrared absorption spectra of the polycondensates obtained in Reference Example 1 and Reference Examples 8 to 9, respectively. Further, the first diagram is a graph showing the change over time in the specific viscosity of the polycondensate solution described in Reference Example 7. Agent Patent Attorney Yoshi 1) Toshio

Claims (1)

[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] (However,
n=2 to 12), and has a specific viscosity ηsp/c(
0.2 mol m-cresol in chloroform solution, 30
A novel polymer complex comprising a transition metal salt complex of a polycondensate exhibiting a value of about 0.2 to 1.5. Claim 1 having 2, 5 or more repeating units
Novel polymer complexes described in Section. 3. General formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] (However,
n=2 to 12), and has a specific viscosity ηsp/c(
0.2 mol m-cresol in chloroform solution, 30
℃) of about 0.2 to 1.5.
A method for producing a novel polymer complex, characterized by reacting it with an aqueous solution of a transition metal salt at a temperature below ℃. 4. The method for producing a novel polymer complex according to claim 3, wherein the complexation reaction is carried out under room temperature conditions.