JPS61138660A - Crown ether composition - Google Patents

Abstract

PURPOSE:A composition that is composed of a specific Schiff base type benzocrown ether and a thermoplastic resin, thus having every excellent selectivity to potassium ions. CONSTITUTION:The objective composition is obtained by combining (A) 0.1-20 pts.wt. of a Schiff base type benzocrown ether of formula I (A is -N=CH-, -CH=N-; R is formula II, III, IV, V, VI, VII, VIII; X is H, halogen, nitro) with (B) 100pts.wt. of a thermoplastic resin. In addition, (C) an organoboron compound of formula IX (Y1, Y2, Y3, Y4 are H, halogen, alkyl, haloalkyl; p1, p2, p3, p4 are 1-5; M is alkali metal) is perferably added in an amount of less than 0.5 mole per mole of the component A. The component a is advantageously synthesized, when an acid catalyst such as boron trifluoride ethyl etherate is added.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a crown ether composition comprising a specific Schiff base type benzo crown ether and a thermoplastic resin and having good selectivity for potassium ions.

[Conventional technology]

Conventionally, compounds that selectively coordinate to potassium ions include benzo-15-crown-5, benzo-18-crown-6, dibenzo-18-crown-6, cyclohexyl, A/-18-crown. Macrocyclic polyethers such as -6 and dipenzo-30-crown-10, and macrocyclic polypeptides such as palinomycin and nonactin are known. Many applications of film-like materials obtained by molding compositions containing these compounds, particularly as potassium electrodes, have been investigated. Potassium electrode is used to measure potassium ion immersion,
In particular, it is used to quantify potassium concentration in serum quickly and easily.

However, most of the potassium electrodes constructed using compositions containing macrocyclic polyethers that have been reported so far do not contain alkali metal ions other than potassium ions,
In particular, the selectivity for sodium ions was not sufficient. The general formulas (a) and (mouth) are slightly below.

It has only been reported that a potassium electrode constructed using a composition containing the compounds represented by (c) and (c) exhibits excellent potassium ion selectivity.

...h (however, yu is a positive integer greater than or equal to 1)...) (however, n is a positive integer greater than or equal to 1)...... (
c) (However, n is a positive integer of 1 or more) However, for any of the above compounds 0), (b) and (c), multi-step reaction operations are required for their production, and each The reaction had the disadvantage of requiring complicated purification operations.

Furthermore, it has been reported that for the compound (iii), it is necessary to carry out the synthesis reaction under extremely dilute conditions in order to avoid side reactions.

The present inventors have conducted various studies in order to synthesize a macrocyclic polyether compound that has an excellent selective regret ability against potassium salts.

As a result, the Schiff base type represented by the following general formula 〇〇 has a much simpler reaction operation than the above general formulas h), (b), and (c) and has excellent selective coordination ability for potassium salts. Discovered benzo crown ether. (Special application 1982
-237938) (where X is a hydrogen atom, a halogen atom, or a nitro group) [Problems to be solved by the invention] The present inventors will conduct further research. As a result of stacking, it was found that the composition consisting of the Schiff base type benzo crown ether represented by the general formula The inventors have discovered that the material can be suitably used as a film-like material constituting a potassium electrode, and have proposed the present invention.

[Means for solving problems]

That is, the present invention provides a group of (2) general formula (I) (wherein A is -N=CH- or -CH=N-, (however, X is a hydrogen atom, a halogen atom, or a nitro group) Schiff base-type benzocrowne ether (an organic group selected from ) 0.1
20 parts by weight and 100 parts by weight of a thermoplastic resin.

The Schiff base type benzo crown ether represented by the general formula (T), which is one of the components of the crown ether composition of the present invention, is a new compound, and can be confirmed to be such a compound by measurement using a conventional method.

(1) Infrared absorption spectrum (IR) The absorption based on the cyclic polyether structure is 1270cIIL-
! Appear strongly near and near 1130 an-”.-C
The absorption peak derived from H=N- bond is 1620 an-
``Appears nearby.

(2) 13C-Nuclear Magnetic Resonance Spectrum When measuring deuterated chloroform as a solvent and a standard substance, a peak derived from the carbon of -N=CH- or -CH=N- bond was found at 160
A peak derived from the methylene carbon of the crown ether ring appears at around 70 ppm near ppHl.

(3) Mass spectrometry By using electrolytic desorption (abbreviated as FD) as a means of mass spectrometry, the molecular ion peak of the compound represented by the general formula σ) of the present invention can be observed.

(Confirmed by comparing the analysis results of elemental analysis carbon, hydrogen, and nitrogen with the theoretical values calculated from the above general formula 〇).

The properties of the compound represented by the general formula 〇) of the present invention are explained below in terms of the manufacturing method, uses, etc. ≠ is clear from the results of the examples, but typical properties are as follows. 0 (T) The Schiff base type benzocrowne ether of the present invention cannot generally be distilled and has a clear boiling point.

■ With normal manufacturing methods, it is obtained as a powdery solid, and it is obtained at room temperature (2.
(5°C), it is a pale yellow to solid in color when it has a polycyclic condensed group.

The melting point is 70-220°C.

(2) The Schiff base type benzocrowne ether represented by the general formula (T) is soluble in various organic solvents. For example, it dissolves in methylene chloride, chloroform, benzene, toluene, acetone, tetrahydrofuran, dioxane, dimethylformamide, methanol, etc. at room temperature. Further, it dissolves in ethanol, isopropyl alcohol, etc. under heating, and further dissolves in heated hexane, heptane, etc. to a maximum extent.

Since the above-mentioned properties can be confirmed very easily, it is sufficient to confirm them in advance before use.

Among the benzo crown ethers made by Shipp base represented by the above general formula ○, compounds in which R has three or more benzene rings condensed, especially compounds in which four benzene rings are condensed, are:
When the crown ether composition of the present invention is used in a potassium electrode, it has good selectivity and sensitivity to potassium ions, so it is suitably used in the present invention.

The method for producing the Schiff base benzo crown ether represented by the general formula σ) of the present invention is not particularly limited, and any method may be employed. A specific example of an industrially suitable method is as follows.

That is, formylbenzo crown ether shown in the general formula plate and the general formula (
IV) A method of reacting an aromatic amine represented by R-NH2(IV) (where R is the same as that explained in general formula (I)) is preferred.

In addition, aminobenzo crown ether represented by the general formula M and general formula (V
l) A method of reacting with an aromatic aldehyde represented by R-CHO(Vl) (wherein R is the same as that explained in the general formula σ) is also suitably employed. These methods may be suitably selected and used depending on the target compound.

In the general formulas shown in ff), (IV), and (capital) above, X is a hydrogen atom, a halogen atom, or a nitro group, as already explained in the general formula (I).

The halogen atoms include chlorine, bromine, and iodine.

Each fluorine atom can be used without particular limitation, but chlorine atoms and bromine atoms are generally preferred from the viewpoint of ease of handling raw materials. In addition, the number of halogen atoms and nitro groups to be substituted is generally one due to the ease of obtaining raw materials.
There is no problem even if a plurality of substitutions ≠ O. The method for producing the raw material compound represented by the general formula (2) is not particularly limited, but may include 3,4-dihydroxybenzaldehyde and tetraethyleneglyfur dichloride. or by reacting catefol with tetraethylene glycol dichloride to obtain the general formula (■
) Any known method in which an aldehyde group is introduced after obtaining a compound represented by formula is suitable.

The method for producing the raw material compound represented by the general formula (V) is not particularly limited, but the known method involves nitrating the compound represented by the general formula (Vl) and then reducing it with hydrogen in the presence of a platinum catalyst or the like. The method is preferably adopted.

The reaction mode for obtaining the compound represented by the general formula 〇 of the present invention is not particularly limited, but it is generally prepared in a solution or suspension state in a solvent that is inert to the aldehyde groups and amino groups possessed by the individual G-Xiao raw materials. A method of directly reacting is preferably employed. Examples of solvents suitably used in the above reaction include aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, and xylene; Aliphatic halogenated hydrocarbons such as 0-loethane; halogenated aromatic hydrocarbons such as chlorobenzene and brombenzene; methanol, ethanol, isopropanol, butanol, engineered ethylene glycol, diethylene glycol.

aliphatic alcohols such as acetone, methyl ethyl ketone, methyl isobutyl ketone, nitriles such as acetonitrile, benzonitrile; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane; esters such as methyl acetate, ethyl acetate, etc. Types: Amides such as formamide, dimethylformamide, dimethylacetamide, and the like.

Although it is possible to obtain the compound represented by the general formula (T) of the present invention without using a special catalyst, a trace amount of an acid catalyst such as boron trifluoride ethyl ether, para-toluenesulfonic acid, sulfuric acid, or phosphoric acid may be used. By adding it, the reaction rate can be significantly increased, which is industrially advantageous.

The reaction temperature employed to obtain the compound represented by the general formula σ) of the present invention is not particularly limited, but is generally 50°C.
It is sufficient if the temperature is between 150°C and 150°C. Further, the reaction time varies depending on the reaction temperature, reaction solvent, raw material concentration, presence or absence of a catalyst, etc., but generally it may be appropriately determined and employed within the range of 10 minutes to 50 hours.

The compound represented by the general formula σ) of the present invention obtained by the above reaction has a high molecular weight and a high boiling point, so it is difficult to distill it.

Therefore, it is usually extracted.

Although it is purified by means such as recrystallization, depending on the reaction solvent, the desired product may selectively precipitate as the reaction progresses.
In some cases, a product of sufficient purity can be obtained by simple filtration without requiring any special post-treatment.

Another component of the crown ether composition of the present invention is a thermoplastic resin. As the thermoplastic resin used in the present invention, known thermoplastic resins can be used without any restriction. When the crown ether composition of the present invention is molded into a W1 material and used as a potassium electrode, it is usually used in an aqueous solution, so it is preferable that the thermoplastic resin is insoluble in water. Examples of thermoplastic resins suitable for use in the present invention include vinyl chloride and vinyl bromide.

Homopolymers or copolymers of vinyl halides such as vinylidene chloride and tetrafluorotetraethylene; styrene, t2
/I/Homopolymers or copolymers of styrene and its substituted products such as styrene and bromostyrene; methyl acrylate,
Homopolymers or copolymers of acrylic esters or methacrylic esters such as acrylic/S/wL ethyl, ethyl methacrylate, butyl methacrylate/l'; homopolymers or copolymers of vinyl esters such as vinyl acetate Diene polymers such as butadiene and isoprene, or copolymers of these dienes with styrene, acrylonitrile, etc.; Polyurethanes; Polymers or copolymers; Cellulose derivatives such as cellulose acetate and cellulose nitrate, etc. It will be done.

The crown ether composition of the present invention is a composition containing a ship base type benzo crown ether represented by the general formula CI) and a thermoplastic resin. The blending ratio of the compound represented by the general formula (I) is not particularly limited as long as it exhibits the desired properties, but generally the thermoplastic resin 100%
0.1 to 20 parts by weight, preferably 1 to 1 parts by weight
It is preferable to use it in a range of 0 parts by weight. The above general formula (T
) If the amount of the compound represented by () is less than the above range, the selectivity for potassium ions tends to decrease, and it may be undesirable as a composition constituting a potassium electrode. In addition, if the amount exceeds the above range, the compound represented by the general formula (T) tends to precipitate, and in severe cases, layer separation occurs between the layer of the above compound and the layer of the thermoplastic resin, and the crown ether composition Generally, this is not preferred as it may cause the product to become non-uniform.

Even when the crown ether composition of the present invention is composed of the above-described ship base type benzo crown ether and a thermoplastic resin, it constitutes a potassium electrode which can be sufficiently put to practical use, as shown in the Examples. However, it is also possible to use the following general formula (10)(Y4)p.

(However, Y The composition of the present invention can be prepared by using an organic boron compound represented by (alkali metal) in a molar ratio of 0.5 or less, preferably in the range of 0.01 to 0.4, to the Schiff base benzocrow ether. When used as a potassium electrode, its measurement sensitivity and lifetime can be improved.

If the amount of the organic boron compound exceeds the above range, the selectivity and sensitivity of potassium ions may be significantly reduced when the crown ether composition of the present invention is used as a potassium electrode, which is not preferable.

In the general formula 0, Yl*Y2*, Y3 and Y4
As the halogen atom represented by, fluorine, #1 element, bromine, and iodine atoms are used. In addition, the general formula ■
The alkyl groups represented by Y□, Y, , Y3, and Y4 are not limited to the number of carbon atoms, but those having 1 to 4 carbon atoms are generally preferred. in particular,
Methyl group.

Examples include ethyl group, rL-propyl group, and nibutyl group. Furthermore, as the herooalkyl group, those in which at least one hydrogen atom of the above-mentioned alkyl group is substituted with a halogen atom can be used without any limitation. Specifically, a fluoromethyl group, a chloromethyl group, a bromoethyl group, a 9-doprobyl group, a chlorobutyl group, a difluoromethyl group, and a dichloroethyl group.

Dibromopropyl group, trifluoromethyl group.

Trichloromethyl group, triptetramupropyl group.

Examples include pentafluoroethyl group 1 and the like.

The organic boron compound represented by the general formula
, Chew, 26.15 (1964) J and “5ynth, React, Inorg, Mat
, -Org.

Chew, 10.261 (1980) J et al.

In the organic boron compound represented by the general formula 0, Yl,
Y2 * Y3 and Y4 are hydrogen atoms, fluorine atoms,
A compound that is a chlorine atom or a trifluoromethyl group is
It is preferably used in the present invention because it is easily available or can be easily derived from a hand-made product by salt exchange to the desired alkali metal salt. Further, in the general formula (0), potassium, rubidium, cesium, etc. are suitable as the alkali metal because they generally have low solubility in water, and potassium is particularly preferred. The alkali metal is lithium.

Sodium generally has high water solubility, so
Depending on the combination of the thermoplastic resin contained in the crown ether composition of the present invention and the Schiff base type benzocrownethyl represented by the general formula σ), the resulting crown ether composition may not meet the intended use ψ Please be careful as there may be cases.

Since the crown ether composition of the present invention contains a thermodegradable resin, it can be formed into any shape depending on the use, for example, a film-like material.
It can be formed into granules, fibers, etc. When formed into a film-like material, the ion-exchange resin acid can be used as an ion-exchange membrane or potassium electrode, and when formed into a granular or fibrous material, the ion-exchange resin acid can be applied as a chromatography material.

When the crown ether composition of the present invention is used below, the thickness of the film-like material is not particularly limited, but is 1
It is sufficient to select it within the range of ~1000 μm. Also,
It is better for the film-like material to have flexibility, and in general, it is preferable that the tensile modulus (25°C) of the film-like material is 5000% or less, particularly 10 to 300%, preferably 50 to 2
000% range is preferably used. Therefore, when using polyurethanes and polysiloxanes as thermoplastic resins, which generally produce flexible film-like materials, these resins can be used as they are, but thermoplastic resins that give film-like materials that are relatively inflexible can be used as they are. Resin such as polyvinyl chloride,
When using materials such as polystyrene, it is best to use a plasticizer. The plasticizer is not particularly limited and any known plasticizer can be used, but in general, the following may be used. For example, dimethyl 7-talate, diethyl phthalate,
Heptatarate esters such as dibutyl heptatalate and dioctyl heptatalate; fatty acid esters such as dioctyl adipate and dioctyl heptabacate; and orthonitrophenyl alkyl ethers such as orthonitrophenyl octyl ether. The amount of these plasticizers to be added may be appropriately selected depending on the purpose of use of the film-like material, but in general, the amount of plasticizer added to 100 parts by weight of the thermoplastic resin is 30 to 3 parts by weight.
It is preferable to select it within the range of 00 weight i parts.

The method for producing the above film-like material is not particularly limited. Typical manufacturing methods that are generally suitably employed are as follows.

α] The compound represented by the general formula (1) is added together with a thermoplastic resin, or a plasticizer, and if necessary, an organic boron compound represented by the general formula 〇 is added, and these are mixed into an organic solvent. A method in which the organic solvent is evaporated to form a film after dissolving and coating or pouring the solution onto the board surface. As the organic solvent, thermoplastic resin and general formula (1
) Any known compound can be used without any restriction as long as it dissolves the compound shown in the formula. Specific examples of organic solvents that are generally suitably used include tetrahydro7rane, dioxane, chloroform, 1,2-dichloroethane, methylene chloride, dimethylformamide, dimethylacetamide, benzene, and toluene.

Furthermore, when adding an organic boron compound represented by the general formula 0, even if the organic boron compound alone is soluble in an organic solvent, if the compound represented by the general formula 〇J coexists, the general formula σ If the molar ratio to the compound shown by is 0.5 or less, solubilization is likely to occur, so it is desirable to select a solvent after carrying out a dissolution test in advance.

■ The compound represented by the general formula ff) is added to a thermoplastic resin, a plasticizer if necessary, and an organic boron compound represented by the general formula (■) above, and the mixture is heated and molded as a raw material to form a film-like material. There is a way to do it. The heat molding method is not particularly limited, and any known method can be employed. For example, the general formula (
A method of melt-extruding a compound represented by I), a thermoplastic resin, or a mixture to which a plasticizer is added as necessary at a temperature equal to or higher than the softening temperature or melting temperature of the thermoplastic resin, and molding the mixture into a film-like product, or the mixture. What is necessary is to adopt a method of forming the material into a film-like material by hot pressing.

The film-like material obtained by the method described above is particularly suitable for use as a film-like material for a potassium electrode. Any known method can be used without particular limitation as to the manner in which the membrane-like material is formed into a potassium electrode. For example, a solution in which the compound represented by the general formula (I) shown in σ) is poured onto a droplet plate, the solvent is removed to form a film-like material, and a film-like material is obtained. A method is to cut out the film-like material to a predetermined size and attach the film-like material to a membrane holder to use it as a potassium electrode.Alternatively, the film-like material is formed directly on the surface of iron wire, platinum wire, etc.
Examples include a method of using it as a potassium electrode.

〔Effect of the invention〕

As described above, the crown ether composition of the present invention has the following features:
It has extremely good selectivity to potassium ions, and the membrane-like material obtained by molding it is ideal as a membrane-like material constituting a potassium electrode. In addition, the crown ether composition containing the Ship base type benzo crown ether of the present invention has a selective transport ability or a selective absorption ability for potassium salts, and can be applied to removal, concentration, etc. of potassium salts. is also possible.

Production Examples and Examples are given below to further specifically explain the present invention, but the present invention is not limited to these Production Examples and Examples.

In the Examples, the performance of an electrode using a membrane obtained by molding the crown ether composition of the present invention was evaluated using the following apparatus and method.

For Examples 1 to 3 and Examples 5 to 7, the 4th Fj!
A membrane material was attached to the membrane holder shown in J, and the electrode performance was evaluated using the apparatus shown in FIG. In Example 4≠
In this case, a platinum wire with a film-like substance formed on the surface as shown in FIG. 5 is used as an electrode, and it is directly attached to the electrode part 1 in FIG.

The electrode performance was evaluated by wearing it.

The selection ratio of potassium ions to sodium ions is determined in "Ion Selective Electrodes" (Kyoritsu Shuppan 1977), Volume 2.
It was determined by the mixed solution method described in Chapter 3. Specifically, in an aqueous solution containing potassium chloride and sodium chloride.
Then, the electromotive force was measured while keeping potassium chloride at a constant concentration (10'-'M) and varying the concentration of sodium chloride. Then, the relationship between electromotive force and sodium chloride concentration was plotted, and the value obtained by dividing the sodium chloride concentration at the inflection point by the potassium chloride concentration was defined as the selection magnification. The higher this value, the better the potassium electrode.

In addition, the electromotive force of a core-containing aqueous solution of potassium chloride alone was measured in the concentration range of 10-1 to 10-'M, and from the relationship between the electromotive force and the potassium chloride concentration, the slope was determined as follows:
mma/+1 as the amount of change in the electromotive force for a double change
Calculated in units of saad. The larger this value is, the higher the sensitivity of the electrode is. Moreover, all measurements were performed at 25°C.

Production Example 1 Ethanol 401E1 in an Erlenmeyer flask with an internal volume of 100 cm containing a magnetic rotor! ! .

The compound represented by (hereinafter simply referred to as eformylbenzo 15
It is abbreviated as Crown 5. ) to z.

, F (6,76 mmol), 1-aminonaphthalene 0.
97 Jil (IL76 mmol) was charged, and the reaction was carried out under reflux for 48 hours using an oil bath while stirring with a cooling tube attached. After the reaction, ethanol was distilled off. The obtained reaction product was recrystallized from isopropanol to give pale yellow crystals L9r.
I got l. The following analysis was performed on the obtained product.

(1) Melting point 99-100℃ <2) Infrared absorption spectrum # (results are attached as Figure 1) -CH=N-1640儂-1 Cyclic ether 12700-"* 113 G C
11-"(a) 13C-Nuclear Magnetic Resonance Spectrum (results are attached as Figure 2) Measurement solvent: deuterated chloroform Standard: deuterated chloroform 1122-149 Pml"i1 1+ 124 PPlI c 160 ppm 4 12911PI11 0111-113 ppm t 152 ppm + g 68-72 ppm (4) Mass spectrometry spectrum FD method m/e = 421 (M”) (5
From the measurement results beyond elemental analysis, it was confirmed that the product was the desired product.

Production Examples 2 to 11 4'-formylbenzo 15 crowns 5t'1 were placed in an eggplant-shaped flask with an internal volume of 100 mm equipped with a cooling tube and a water metering receiver.
01 (6,76i!Jmo#), 6.76 mmol of aromatic amine represented by the general formula R-NH2 shown in Table 1 (however, only R is shown in Table 1), and reacted. As a catalyst, 20% of boron trifluoride ethyl ether and 501,117% of benzene were charged, and azeotropic dehydration was carried out for 4 hours while stirring with a magnetic rotor and heating with an oil bath.

After the reaction, benzene was distilled off and the product was recrystallized from isopropyl alcohol to obtain yellow colored crystals. The yield, melting point, and elemental analysis results of the reactants are summarized in Table 1.

The products obtained in Production Examples 2 to 10 in Table 1 below were determined to be the desired products by the analysis method described in Production Example 1.

Production Examples 11 to 13 4'-aminobenzo 15 crowns 5 were added to λoJ in a red eggplant-shaped flask with an internal volume of 100 equipped with a cooling tube and a water metering receiver.
(9,ss millimo/L/), general formula R shown in Table 2
Using the aromatic aldehyde represented by -CHO (however, only R is shown in Table 2) as a 9.85" rimole 2 reaction catalyst, boron trifluoride ethyl ether is used as 2CIsFI.
and benzene were charged and azeotropically dehydrated for 4 hours while stirring with a magnetic rotor and heating in an oil bath. After the reaction, benzene was distilled off and the product was recrystallized from Impropatool. The reaction product was analyzed by the same method as described in Production Example 1, and it was confirmed that the product was the desired product. The results are shown in Table 2.

Table 2 Example 1 Table 3 shows the compound 10η represented by the general formula (T) obtained in Production Examples 1 to 13, the thermoplastic resin, and the plasticizer. The composition was dissolved in 10ml of tetrahydro7ran. This solution was cast on a smooth glass plate, and then 7 strands of tetrahydrocarbons were evaporated to obtain a film with a thickness of about 100 microns. The electrode performance of the film-like material constructed using these film-like materials was evaluated in the third
The electrode performance is shown in the table.

Example 2 Schiff base type benzo crown ether 2 shown in Table 4
0η and 600 mg of poly(bisphenol octacarbonate)-poly(dimethylsiloxane) block copolymer (composition 49:51 weight ratio) were dissolved in methylene chloride at 20 eC.

After this solution was cast onto a smooth glass plate surface, the methylene chloride was evaporated to obtain a film with a thickness of about 100 μm. Table 4 shows the performance of electrodes constructed using these membrane materials.

Table 4 Example 3 20 Mg of the compound obtained in Production Example 9.

Place polyvinyl chloride 200■ and orthonitrophenyl octyl ether 40019 in a small glass petri dish.
After thoroughly mixing using microspertyl on a hot plate heated to 120"C, the compound was heated to about 70 μm by heat press.
It was molded into a film-like product with a thickness of m. The performance of the force IJ-um electrode constructed using this film-like material is that the selection magnification is 1800° gradient 53
mv/decade.

Example 4 Shipp base type benzo crown ether 2 shown in Table 5
0 to 9, a thermoplastic resin and a plasticizer were dissolved in 3d tetrahydro 7 run with the composition shown in Table 5. After immersing platinum f1 having an outer diameter of 110 seconds in this solution, it was taken out from the solution and allowed to stand for 10 minutes to evaporate the solvent, tetrahydrofuran. This operation was repeated 10 times to form a film on the platinum wire. In order to avoid contact between the measurement solution and the platinum wire, the exposed platinum portion was covered with a tape made of tetrafluoroethylene. The outline of this platinum wire coated with a film-like substance is shown in Section 5.
As shown in the figure. The electrode performance of these film-covered platinum wires was evaluated. The results are shown in Table 5 as electrode performance.

Noji, *' Lower margin Example 5 Compound 20119 represented by the general formula σ) obtained in Production Examples 1 to 13 and thermoplastic resin 200Q.

and plasticizer 300119 and the organic boron compound represented by the general formula 〇 are dissolved in 1.2-dichloroethane 10- in a predetermined molar ratio to the compound represented by the general formula 〇), and then cast onto a glass plate, The 1,2-dichloroethane was evaporated to obtain a film about 100 μm thick. Table 6 shows the electrode performance of the potassium electrode constructed using the obtained film-like material. As shown in Table 6, the addition of the organic boron compound resulted in an extremely high gradient of 58 to 60 mm, and it is clear that a highly sensitive potassium electrode could be constructed.

Example 6 Compound 20 of Production Example 9, Polyvinyl chloride 200 9.
Orthonitrophenyl octyl ether 400119.
(Add 0.1 molar amount of $BK to the compound of Production Example 9 in a small glass petri dish, mix well using a microspertyl on a hot plate heated to 120°C, and then add the compound to the compound of Production Example 9.) was formed into a film-like material with a thickness of about 80 μm by hot pressing.The electrode performance of the potassium electrode constructed using this film-like material was as follows: selection magnification of 2800° gradient of 59 mv/de
cade was 0 or more with a margin of 1,000.Example 7 A film was constructed using the film-like material obtained in Example 1-7 (consisting of the metal compound of Production Example 9, polyvinyl chloride, and orthonitrophenyl octyl ether). Potassium electrode and Example 5
Film-like material obtained in A9 (compound of Production Example 9 and polyvinyl chloride and orthonitrophenyl octyl ether and (@
+BK)
31 (DO, 15M NaCJ.

Immersed in an aqueous solution containing 0.003MK (J at 30°C,
The performance of the electrodes was taken out every two weeks and the durability of both electrodes was examined. The results are shown in Table 7.

Table 7 It is clear from Table 7 that the durability of the potassium electrode can be greatly improved by adding an organic boron compound.

[Brief explanation of drawings]

FIG. 1 and FIG. 2 are an infrared absorption spectrum and an IH@magnetic resonance spectrum of the compound obtained in Example 1, respectively. FIG. 3 is an explanatory diagram of an apparatus for measuring electromotive force, and FIG. 4 is an explanatory diagram showing various components that can be built into the electrode 1 of FIG. 3. FIG. 5 is a schematic diagram of a platinum wire coated with the film-like material of the present invention. In FIG. 3, FIG. 4, and FIG. 5, each number indicates the following content. DESCRIPTION OF SYMBOLS 1... Electrode, 2... Measurement solution, 3... Magnetic rotor, 4... Magnetic stirrer, 5... 1M lithium acetate salt bridge, 6... Potassium chloride saturated aqueous solution, 7...・Saturation electrode, 8... Electrometer (Hokuto HE-
103 type), 11... Acrylic film holder, 12-
・"Silver I, No. 13 S coated glass tube, 14...Silver-silver chloride internal standard electrode. 15...10-3M potassium chloride internal standard solution, 16.
...Membrane-like material, 17.-0-IJ song 21...Platinum wire, 22...Membrane-like material, 23...Teflon tape.

Claims (2)

[Claims] (1) (A) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, A is -N=CH- or -CH=N-, and R is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, X is hydrogen atom, a halogen atom, or a nitro group)) 0.1
-20 parts by weight and (B) 100 parts by weight of a thermoplastic resin. (2) (A) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, A is -N=CH- or -CH=N-, and R is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, X is a hydrogen atom, a halogen atom, or a nitro group) Schiff base type benzocrowne ether 0.1
~20 parts by weight (B) 100 parts by weight of thermoplastic resin and (C) the above Schiff base type benzo crown ether in an amount of 0.5 or less in molar ratio of the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, Y_1, Y_2, Y_3 and Y_4 are the same or different hydrogen atoms, halogen atoms, alkyl groups or haloalkyl groups, p_1, p_2, p_3 and p_4 are the same or different integers from 1 to 5, and M is A crown ether composition mainly consisting of an organic boron compound represented by (alkali metal).