JPH0124824B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a cyclic polyether composition comprising a novel cyclic polyether compound and a thermoplastic resin, and particularly exhibiting sodium ion selectivity. [Prior Art and Problems to be Solved by the Invention] Conventionally, from the standpoint of separation and analysis of sodium ions, organic compounds that selectively and strongly coordinate with sodium ions have been required. Typical research has focused on antibiotics such as monensin, but these have low selectivity toward other alkali metals, especially potassium, and have therefore not been of practical use.
Another example of research is the 12-crown structure shown below.
A cyclic polyether having a skeleton of 4 is known. (Below, the skeleton of 12-Crown-4 is

[Means and effects for solving problems]

The present inventors have conducted various studies in order to synthesize a cyclic polyether that has excellent selective coordination ability for sodium ions and is hydrophobic.
As a result, we succeeded in obtaining a cyclic polyether compound with far superior sodium-selective coordination ability compared to the structural formulas (A) and (B), which we have already proposed (Japanese Patent Application No. 172-287-1987). issue). As a result of further research, the present inventors discovered that a composition consisting of a cyclic polyether compound represented by the above general formula () and a thermoplastic resin is a particularly useful material as a sodium electrode. The invention was completed. That is, the present invention comprises (1) (A) 100 parts by weight of thermoplastic resin and (B) general formula [] [However, A is

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or

[Formula] (where, X is a halogen atom or a halogenoalkyl group, R is a hydrogen atom or an alkyl group, m
is an integer of 0 to 20, and n is an integer of 1 to 5. ), B represents (-CH ₂ )- _l CH ₂ -O-CH ₂ -,

[Formula] −O(−CH ₂ ) − _l+1 CH ₂ −O−CH ₂ −,

[Formula] or

[Formula] (However, l is an integer of 0 to 7.) ] This is a cyclic polyether composition mainly consisting of 0.1 to 40 parts by weight of a cyclic polyether compound represented by: In the general formula [], each of fluorine, chlorine, sulfur, and iodine atoms can be used as the halogen atom represented by X. Further, as the halogenoalkyl group represented by X, the alkyl groups substituted with the above-mentioned halogen atoms can be used without any restriction. In particular, perhalogenated alkyl groups such as trifluoromethyl group, pentafluoroethyl group, trichloromethyl group, and pentachloroethyl group are preferably used. In the general formula [], the halogenoalkyl group represented by X and the alkyl group represented by R are not limited in number of carbon atoms, but preferably have 1 to 4 carbon atoms.
are used. When the cyclic polyether compound represented by the above general formula [] is used in a sodium-selective electrode, the selectivity to sodium ions and water resistance are somewhat affected by the type of A in the general formula []. receive. In order to improve sodium selectivity and water resistance, A in the general formula [] preferably satisfies either (1) or (2) below. (1) Having two or more aromatic nuclei. (2) It has one aromatic nucleus, and the aromatic nucleus is substituted with three or more halogen atoms or halogenoalkyl groups. Furthermore, it is preferable that A in the general formula [] is a compound that satisfies any of the following (3) to (5). (3) Having three or more aromatic nuclei. (4) Among those with two aromatic nuclei,

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Must be one of the following. (5) It has one aromatic nucleus, and the aromatic nucleus is substituted with four or more halogen atoms or halogenoalkyl groups. Regarding B in the above general formula [], if the number of l is large, the difficulty of synthesis and purification may increase or the sodium selectivity may decrease slightly, so it is preferably 4 or less, more preferably It is desirable that it be an integer of 3 or less. The cyclic polyether compound represented by the general formula [ ] of the present invention is a new compound, and can usually be identified as such by the following measurements. (1) Infrared absorption spectrum The absorption based on the structure of 12-crown-4 is 1140,
It appears strongly around 1080 to 1020 cm ^-1 . (2) ¹ H-Nuclear Magnetic Resonance Spectrum When measured in deuterated chloroform solvent using tetramethylsilane as a standard, 12-crown-
The peak derived from H of -CH ₂ -O- in the 4 skeletons is
The absorption peak of hydrogen atoms is around 3.3ppm to 4.2ppm, and when hydrogen atoms are included in the aromatic ring.
It appears at 6.6 ppm to 8.2 ppm, and the relative intensity ratio of these peaks matches the ratio of the number of hydrogens bonded to each group calculated from the above general formula []. (3) Mass spectrometry Field desorption method (hereinafter referred to as FD) is a method of mass spectrometry.
By using this method, the molecular ion peak of the compound represented by the general formula [] of the present invention can be observed. (4) Elemental analysis The amounts of carbon, hydrogen, nitrogen, and halogen in the compound calculated from the above general formula [] almost match the amounts of each element as determined by the analysis. Typical properties of the compound represented by the above general formula [] are as follows. (1) The cyclic polyether compound used in the present invention generally cannot be distilled and it is difficult to obtain a clear boiling point. (2) The cyclic polyether compound used in the present invention is a highly viscous liquid at room temperature, but if A in the general formula [] has 3 or more aromatic nuclei or n has 2 or more In this case, it often becomes a white or yellowish-white solid, and when it contains -N=N-, it becomes an orange solid, and when it contains iodine, it tends to be brownish. The solubility of the cyclic polyether compound represented by the general formula [] differs slightly depending on the types of A and B, but includes methylene chloride, chloroform, benzene, toluene, acetone, tetrahydrofuran, dioxane, dimethylformamide, Many of methanol, ethanol, etc. dissolve at room temperature. Almost insoluble in water. Since these properties can be confirmed very easily, they can be confirmed in advance before use. The method for producing the cyclic polyether compound represented by the general formula [] used in the present invention is not particularly limited, and any method may be employed. Specific examples of industrially suitable methods are as follows. (i) In the above general formula [], B is (-CH ₂ ) _-l
CH ₂ −O−CH ₂ −,

[Formula] −O(−CH ₂ )− _l+1 CH ₂ −O−CH ₂ −, or

In the case of [formula], general formula [] The compound represented by (hereinafter referred to as hydroxymethyl-
12-crown-4) with any one of the following general formulas [], [], or []. A(-O- _CH2 ) _-k ( _-CH2 ) _{-l CH2} -X [] (However, A and l are the same as the general formula [], X is a halogen atom, and k is 0 or 1.) (However, A and l are the same as in the general formula [], X represents a halogen atom, and k is 0 or 1.) (However, A and l are the same as in the general formula [], and k is 0 or 1.) (ii) Also, in the above general formula [], B is

If [formula], general formula [] (However, l is the same as the general formula [].) The compound represented by the general formula [] (However, A is the same as the general formula [], and X
is a halogen atom. ) can be obtained by reacting with an acid halide shown in The compound represented by the above general formula [] is hydroxymethyl-12 represented by the above general formula []
It can be obtained by reacting -crown-4 and ω-aminoalkylcarboxylic acid [ _H2N - _CH2 ( _-CH2 ) _-lCOOH ] in the presence of an acid catalyst. (iii) Furthermore, in the general formula [], B is (-
CH ₂ ) − _l CH ₂ −O−CH ₂ −,

[Formula] −O(−CH ₂ ) − _l+1 CH ₂ −O−CH ₂ − or

〔Effect of the invention〕

As mentioned above, the cyclic polyether composition of the present invention has extremely good selectivity for sodium ions, and a film formed from the same is ideal as a film forming a sodium electrode. . In particular, a cyclic polyether composition containing an organic boron compound has excellent selectivity and sensitivity for sodium ions, and also has excellent durability when used as a sodium electrode. In addition, the composition containing the cyclic polyether compound of the present invention has the ability to selectively transport or selectively absorb sodium salts, and can be applied to the removal and even concentration of sodium salts. 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 Examples, the performance of an electrode using a film-like material obtained by molding the composition of the present invention was evaluated using the following apparatus and method. For Examples 1 to 4 and Examples 6 to 8, the second
A membrane material was attached to the membrane holder shown in Figure 2, and the electrode performance was evaluated using the apparatus shown in Figure 21. In Example 5, an electrode having a film-like material formed on the surface of a platinum wire as shown in FIG. 23 was used as an electrode, and the electrode performance was evaluated by directly attaching it to the electrode part 1 in FIG. 21. The selectivity of sodium ions over potassium ions was determined by the mixed solution method described in Chapter 2, Section 3 of "Ion Selective Electrodes" (Kyoritsu Shuppan, 1977). Specifically, in an aqueous solution containing potassium chloride and sodium chloride, the electromotive force was measured while keeping the concentration of sodium chloride constant (10 ^-4 M) and varying the concentration of potassium chloride. Then, the relationship between electromotive force and potassium chloride concentration was plotted, and the value obtained by dividing the potassium chloride concentration at the inflection point by the sodium chloride concentration was determined as the selection magnification. The higher this value, the better the sodium electrode. In addition, we measured the electromotive force of an aqueous solution containing only sodium chloride in the concentration range of 10 ^-1 to ^{10 -5} M, and from the relationship between the electromotive force and the sodium chloride concentration, we calculated the slope for a 10-fold change in the sodium chloride concentration. The amount of change in electromotive force was determined in mV/decade. The larger this value is, the higher the sensitivity of the electrode is. Furthermore, all measurements were performed at 25°C. Production Example 1 Into a 100 ml eggplant-shaped flask equipped with a cooling tube, 5 mmol of p-chloromethylbiphenyl, 5 mmol of hydroxymethyl-12-crown-4, and 5 mmol of potassium hydroxide were charged.
The mixture was heated to reflux in acetone for 96 hours. After the reaction was cooled and neutralized with hydrochloric acid, the resulting salt was filtered off, and the solvent was removed using a rotary evaporator. The obtained product was separated using a column packed with silica gel (trade name: Wakogel C-200) using ethyl acetate as a developing solvent, and a compound represented by the following structural formula 0.78
g (yield 42%) was obtained. The following analysis was performed on the obtained product. (1) Infrared absorption spectrum (results are attached as Figure 1) Aromatic ring 3000-3100cm ^-1 Cyclic ether 1020-1160cm ^-1 (2) ¹ H-nuclear magnetic resonance spectrum (results are attached as Figure 2) ) Measurement solvent: Deuterated chloroform Standard material: Tetramethylsilane (In the following examples, the determination solvent and standard material are the same as in this example, so their description will be omitted.) The ratio of hydrogen amounts obtained by integration agreed with that of the target product. (3) Mass spectrometry spectrum FD method m/e=372 (M ⁺ ) (4) Elemental analysis

[Table] From the above measurement results, it was confirmed that the product was the desired product. Production Examples 2 to 29 Compounds represented by the general formula [ ] were synthesized from a compound having an ω-chloro group and hydroxy-12-crown-4 in the same manner as in Production Example 1, and are shown in Table 1. The compounds synthesized in Production Examples 2 to 29 were confirmed to be target compounds in the same manner as Production Example 1. For reference, the infrared absorption spectrum and ¹ H-nuclear magnetic resonance spectrum of Production Example 6 are shown in FIGS. 3 and 4, respectively.

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[Table] Production example 30 In a eggplant-shaped flask with an internal volume of 100 ml attached to a cooling tube, add 5 mmol of hydroxymethyl 12-crown-4, 5 mmol of triethylamine, dry N,
50 ml of N-dimethylformamide (hereinafter abbreviated as DMF) was charged, and then 5 mmol of p-azobenzenecarboxylic acid chloride was added. 48 at 70℃
After reacting for an hour, the mixture was cooled, the resulting precipitate was filtered off, and DMF was distilled off using a rotary evaporator. The product was extracted using ethyl acetate as a developing solvent.
Separation and purification was performed using a column packed with silica gel (trade name: Wako Gel C-200) to obtain 1.25 g (yield: 60%) of a compound represented by the following structural formula. The analysis results are listed below. (1) Infrared absorption spectrum (results are attached as Figure 5) Aromatic ring 3000~3100cm ^-1 Cyclic ether 1020~1160cm ^-1 Ester 1720cm ^-1 (2) ¹ H-nuclear magnetic resonance spectrum (results are attached as Figure 5) attached as a diagram) (3) Mass spectrometry spectrum FD method m/e=414 (4) Elemental analysis

[Table] From the above measurement results, it was confirmed that the product was the desired product. Production Examples 31-59 In the same manner as Production Example 30, general formula [] was prepared from an acid chloride compound and hydroxy-12-crown-4. The compound shown was synthesized. The results are summarized in Table 2. For these compounds, see Preparation Example 30.
It was analyzed using the same method as above and confirmed to be the target compound. For reference, the infrared absorption spectrum and ¹ H-nuclear magnetic resonance spectrum of Production Example 32 are shown in FIGS. 7 and 8, respectively.

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[Table] Production example 60 In a 100 ml eggplant-shaped flask equipped with a condenser and a moisture meter, add 50 ml of toluene, 5 mmol of 2,4-dichlorophenylacetic acid, and 12-crown hydroxyl.
4:5 mmol and 2.5 mmol of p-toluenesulfonic acid monohydrate were charged, heated under reflux for 96 hours, and the produced water was removed by azeotropic dehydration. After the reaction, the mixture was neutralized with sodium hydroxide, 25 ml of water was added, the toluene layer was separated, and the toluene was distilled off using a rotary evaporator. The product was separated and purified using a column packed with silica gel (Wako Gel C-200) using ethyl acetate as a solvent, and a compound represented by the following structural formula was obtained. 1.01 g (yield 51%) was obtained. The following analysis was performed on the obtained compound. (1) Infrared absorption spectrum (results are shown in Figure 9) Aromatic ring 3050~3100cm ^-1 Cyclic ether 1020~1160cm ^-1 Ester 1740cm ^-1 (2) ¹ H-Nuclear magnetic resonance spectrum (results shown in Figure 9)
Shown as a diagram. ) (3) Mass spectrometry spectrum FD method m/e = 392, 394, 396 (M ⁺ ) These are isotopes based on Cl ³⁵ Cl ³⁷ . (4) Elemental analysis

[Table] From the above measurement results, it was confirmed that the product was the desired product. Production Examples 61-82 Compounds represented by the general formula [] were synthesized from a carboxylic acid compound and hydroxy 12-crown-4 in the same manner as in Production Example 60. Table 3 summarizes the results. These compounds were analyzed using the same method as in Production Example 60, and it was confirmed that they were the desired products.

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[Table] Production Example 83 30 mmol of pentachlorophenol, 30 mmol of potassium hydroxide, and 300 mmol of ethylene dibromide were added to a 200 ml eggplant-shaped flask equipped with a cooling tube, and the mixture was heated and refluxed in acetone for 96 hours. After the reaction, the reaction mixture was neutralized with hydrochloric acid, the resulting salt was filtered off, and acetone and excess ethylene dibromide were distilled off using a rotary evaporator. The product was recrystallized from isopropyl alcohol to obtain 4.5 g (yield: 40%) of a compound represented by the following structural formula. 5 mmol of the compound, and hydroxymethyl-
5 mmol of 12-crown-4 and 5 mmol of potassium hydroxide were placed in a 100 ml eggplant-shaped flask equipped with a condenser, and heated under reflux for 96 hours. After the reaction, the reaction mixture was neutralized with hydrochloric acid, the resulting salt was filtered out, and the solvent was concentrated using a rotary evaporator, followed by separation and purification using a column packed with silica gel (Wako Gel C200) using ethyl acetate as a solvent. The result was 0.89g of the compound shown by the following structural formula (yield 36
%) was obtained. The following analysis was performed on the obtained compound. (1) Infrared absorption spectrum (results are shown in Figure 11) Cyclic ether 1020-1160 cm ^-1 (2) ¹ H-nuclear magnetic resonance spectrum (results are shown in Figure 12)
Shown as a diagram. ) (3) Mass spectrometry spectrum m/e = 496, 498, 500, 502, 504 (M ⁺ ) These are isotopes based on Cl ³⁵ and Cl ³⁷ . (4) Elemental analysis

[Table] The above results confirmed that the product was the desired product. Production Examples 84 to 164 In the same manner as Production Example 83, cyclic polyether compounds represented by the general formula () were synthesized. The results are summarized in Table 4. For reference, manufacturing example 105
The infrared absorption spectrum and ¹ H-nuclear magnetic resonance spectrum are shown in FIGS. 13 and 14, respectively.

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[Table] Production example 165 A 200 ml eggplant-shaped flask equipped with a cooling tube was charged with 30 mmol of 2,4,5-trichlorophenol, 30 mmol of potassium hydroxide, 30 mmol of ethyl chloroacetate, and 100 ml of acetone, and the mixture was heated for 96 hours. The mixture was heated to reflux. After the reaction, the reaction mixture was neutralized with hydrochloric acid, the resulting salt was filtered off, and the solvent was distilled off using a rotary evaporator. Mix the product with 100ml of acetone, 20ml of water, and 10ml of hydrochloric acid.
ml of the mixed solution was heated at 50°C for 10 hours to hydrolyze the ester. After the reaction, the solvent was distilled off and recrystallization was performed from toluene to obtain 8.3 g (yield: 92%) of a compound represented by the following general formula. 5 mmol of this compound, 5 mmol of hydroxy 12-crown-4, and 2.5 mmol of p-toluenesulfonic acid were placed in a 100 ml eggplant-shaped flask equipped with a condenser and a moisture meter, and heated and refluxed in toluene. , the water produced was removed. After the reaction, cool, add 50 ml of water to neutralize, separate the organic layer and remove toluene using a rotary evaporator, separate and purify the product using ethyl acetate as a solvent and a column packed with silica gel (Wako Gel C200). 1.11g of the compound shown by the following structural formula
(yield 50%). The following analysis was performed on the obtained compound. (1) Infrared absorption spectrum (results are shown in Figure 15) Aromatic ring 3100 cm ^-1 Cyclic ether 1020 to 1160 cm ^-1 Ester 1750 cm ^-1 (2) ¹ H-Nuclear magnetic resonance spectrum (results shown in Figure 16)
Shown as a diagram. ) (3) Mass spectrometry spectrum m/e=442, 444, 446, 448 These are Cl ³⁵ ,
It is an isotope due to Cl ³⁷ . (4) Elemental analysis

[Table] From the above results, it was confirmed that the product was the desired product. Production Examples 166-230 Compounds represented by the general formula () were synthesized by esterification reaction in the same manner as in Production Example 165. The results are summarized in Table 5. These synthesized compounds were analyzed in the same manner as in Production Example 165, and were confirmed to be the desired products. For reference, the infrared absorption spectrum and ¹ H
- Nuclear magnetic resonance spectra are shown in FIGS. 17 and 18, respectively.

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[Table] Production example 231 In a eggplant-shaped flask with an internal volume of 200 ml equipped with a cooling tube, 50 mmol of hydroxymethyl-12-crown-4, 50 mmol of glycine, and 75 mmol of p-toluenesulfonic acid were charged, and 12 mmol of p-toluenesulfonic acid was added in toluene.
The mixture was heated and refluxed for a period of time. After reaction, cool and add 100ml of water.
was added and neutralized with sodium hydroxide, the organic phase was separated, and toluene was distilled off. To the product, 100 ml of chloroform and 50 ml of water were added, and while stirring, sodium hydroxide was added until the pH became slightly basic. The organic phase was separated and chloroform was distilled off to obtain 8.4 g (yield: 65%) of a compound represented by the following structural formula. 4 mmol of this compound and 4 mmol of triethylamine were placed in an eggplant-shaped flask with an internal volume of 100 ml.
4 mmol of azobenzene-p-carbonyl chloride was added and stirred in DMF for 2 hours at room temperature.
After the reaction, the produced salt was filtered off, and dimethylformamide was distilled off using a rotary evaporator. The product was separated and purified using a column packed with silica gel (Wakogel C-200) using ethyl acetate as a solvent.
0.5g of the compound represented by the following structural formula (yield 27%)
I got it. The following analysis was performed on the compound concerned. (1) Infrared absorption spectrum (results are shown in Figure 19) Aromatic ring 3100cm ^-1 Cyclic ether 1040-1160cm ^-1 Amide bond 1720cm ^-1 (2) ¹ H-nuclear magnetic resonance spectrum (results shown in Figure 19)
Shown as a diagram. ) (3) Mass spectrometry spectrum m/e=471 (M ⁺ ) (4) Elemental analysis

[Table] The target object was confirmed from the above results. Production Examples 232-280 Hydroxy-12-
By the reaction of crown-4 with β-alanine and 3-aminobutyric acid, respectively was synthesized. By reacting these compounds with various acid chlorides, compounds represented by the general formula () were synthesized in the same manner as in Example 231.
The results are shown in Table 6. The synthesized compound was analyzed in the same manner as in Example 231, and it was confirmed that it was the desired compound.

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[Table] Example 1 20 mg of cyclic polyether compound obtained in Production Examples 1 to 280, polyvinyl chloride (average degree of polymerization 1100)
200mg, o-nitrophenyl octyl ether 400
mg was dissolved in 10 ml of tetrahydrofuran. After this solution was cast onto a smooth glass plate, the tetrahydrofuran was evaporated to obtain a film with a thickness of about 100 μm.
This membrane was mounted as shown in FIG. 22, and the electrode performance was evaluated using the apparatus shown in FIG. The results are shown in Table 7. In addition, as a comparative example, compounds A and B represented by the following structural formula, which are conventional sodium-selective substances, were used.
The test was conducted in the same manner, and the results were reported in the 7th test.
Shown in the table.

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[Table] Example 2 20 mg of the cyclic polyether compound shown in Table 8 and poly(bisphenol A carbonate)-poly(dimethylsiloxane) block copolymer (composition
49:51 weight ratio) was dissolved in 20 c.c. of methylene chloride. After this solution was cast on a smooth glass plate, the methylene chloride was evaporated to obtain a film about 100 microns thick. Table 8 shows the performance of electrodes constructed using these membrane materials.

[Table] Example 3 10 mg of the cyclic polyether compound shown in Table 9, a thermoplastic resin, and a plasticizer were used in the composition shown in Table 9.
Dissolved in 10ml of tetrahydrofuran. After this solution was cast on a smooth glass plate, the tetrahydrofuran was evaporated to obtain a film about 100 microns thick. The performance of electrodes constructed using these membrane materials is shown in Table 9. In addition, hereinafter, the thermoplastic resin and plasticizer will be abbreviated as follows. Polyvinyl chloride: PVC Polymethyl methacrylate: PMMA Polystyrene: PSt Polyvinylidene chloride: PVDC Ortho-nitrophenyl octyl ether:
NPOE Dibutyl phthalate: DBP Dioctyl phthalate: DOP Dioctyl adipate: DOA Dioctyl sebacate: DOS

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[Table] Example 4 20 mg of the compound obtained in Production Example 9, 200 mg of polyvinyl chloride, and 400 mg of orthonitrophenyl octyl ether were placed in a small glass tray.
After thorough mixing using a micro spatula on a hot plate heated to 120° C., the mixture was formed into a film-like material with a thickness of about 70 μm by hot pressing. The performance of the sodium electrode constructed using this membrane-like material is that the selection magnification is 40,
The gradient was 51 mV/decade. Example 5 20 mg of the cyclic polyether compound shown in Table 10
The thermoplastic resin and plasticizer were dissolved in 3 ml of tetrahydrofuran with the composition shown in Table 10. After immersing a platinum wire with an outer diameter of 0.5 mm in this solution for 10 seconds,
It was taken out from the solution and left for 10 minutes to evaporate the solvent, tetrahydrofuran. This operation was repeated 10 times to form a film on the surface of the platinum wire.
In order to avoid contact between the measurement solution and the platinum wire, the exposed platinum part was covered with a tape made of tetrafluoroethylene. FIG. 23 shows an outline of this platinum wire coated with a film-like material. The electrode performance of these film-covered platinum wires was evaluated. The results are shown in Table 10 as electrode performance.

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[Table] Example 6 20 mg of the cyclic polyether compound shown in Table 11, 200 mg of the thermoplastic resin, 300 mg of the plasticizer, and the organic boron compound represented by the general formula () were added at a predetermined molar ratio to the cyclic polyether compound. After dissolving in 10 ml of 1,2-dichloroethane, it was cast onto a glass plate, and the 1,2-dichloroethane was evaporated, leaving about
A film-like material with a thickness of 100 μm was obtained. Table 11 shows the electrode performance of the sodium electrode constructed using the obtained film-like material. As shown in Table 11, addition of an organic boron compound increases the selectivity by 10 to 40 times, and the slope shows an extremely high value of 58 to 60 mV, clearly indicating that a highly sensitive sodium electrode can be constructed. .

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[Table] Example 7 15 mg of the compound of Production Example 8, 200 mg of polyvinyl chloride,
Orthonitrophenyl octyl ether 400mg,

[Formula] was added in a molar ratio of 0.1 to the compound of Production Example 8 in a small glass jar,
After thorough mixing using a micro spatula on a hot plate heated to 120° C., the mixture was hot pressed to obtain a film-like material with a thickness of about 90 μm. The performance of the sodium electrode constructed using this membrane material was a selection factor of 50 and a slope of 59 mV/decade. Example 8 A sodium electrode constructed using the film-like material obtained in Example 1 No. 39 (consisting of the compound of Production Example 39, polyvinyl chloride, and orthonitrophenyl octyl ether), and the membrane material obtained in Example 6 No. 39. film-like substance (compound of Production Example 39 and polyvinyl chloride and orthonitrophenyl octyl ether and

A sodium electrode constructed using [formula]
The electrodes were immersed in an aqueous solution containing KCl at 30°C and taken out every two weeks to measure electrode performance and examine the durability of both electrodes. The results are shown in Table 12.

【table】 [Brief explanation of drawings]

Figure 1, Figure 3, Figure 5, Figure 7, Figure 9, Figure 11, Figure 13, Figure 15, Figure 17, and Figure 1.
Figure 9 shows the infrared absorption spectrum of the cyclic polyether compound used in the present invention. Moreover, FIG. 2, FIG. 4, FIG. 6, FIG. 8, FIG. 10, FIG. 12, FIG. 14, FIG. 16, FIG. 18 and FIG. 20 show the cyclic polyether compounds of the present invention. The ¹ H-nuclear magnetic resonance spectrum of . FIG. 21 is an explanatory diagram of the device for measuring electromotive force, and FIG. 22 is an explanatory diagram of the device for measuring electromotive force.
FIG. 2 is an explanatory diagram showing various components built into the.
FIG. 23 is a schematic diagram of a platinum wire coated with a film containing the cyclic polyether compound of the present invention. In FIG. 21, FIG. 22, and FIG. 23, each number indicates the following content. DESCRIPTION OF SYMBOLS 1... Electrode, 2... Measurement solution, 3... Magnetic rotor, 4... Magnetic stirrer, 5... 0.1M lithium acetate salt bridge, 6... Potassium chloride saturated aqueous solution, 7...
Saturated electrode, 8... Electrometer (Hokuto HE-103 type), 11... Acrylic membrane holder, 12... Silver wire, 13... Covered glass tube, 1
4...Silver-silver chloride circular standard electrode, 15...10 ^-3 M
Sodium chloride internal standard solution, 16... Membrane-like material containing a cyclic polyether compound, 17... O-ring, 21... Platinum wire, 22... Membrane-like material containing a cyclic polyether compound, 23... Made of Teflon tape.

Claims (1)

[Claims] 1 (A) 100 parts by weight of thermoplastic resin and (B) General formula [] [However, A is [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] or [Formula] (where X is a halogen atom or a halogenoalkyl group,
R is a hydrogen atom or an alkyl group, m is 0-
It is an integer of 20, and n is an integer of 1 to 5. ), B represents (-CH ₂ )- _l CH ₂ -O-CH ₂ -,
[Formula] −O(−CH ₂ ) − _l+1 CH ₂ −O−CH ₂ −,
[Formula] or [Formula] (where l is an integer of 0 to 7). ] Cyclic polyether compound represented by 0.1-40
A cyclic polyether composition consisting mainly of parts by weight. 2 (A) 100 parts by weight of thermoplastic resin (B) General formula [] [However, A is [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] or [Formula] (where X is a halogen atom or a halogenoalkyl group,
R is a hydrogen atom or an alkyl group, m is 0-
It is an integer of 20, and n is an integer of 1 to 5. ), B represents (-CH ₂ )- _l CH ₂ -O-CH ₂ -,
[Formula] −O(−CH ₂ ) − _l+1 CH ₂ −O−CH ₂ −,
[Formula] or [Formula] (where l is an integer of 0 to 7). ] Cyclic polyether compound represented by 0.1-40
Parts by weight and (C) the following general formula [] in an amount of 0.01 to 0.5 in molar ratio to the cyclic polyether compound of (B) above. (However, Y ₁ , Y ₂ , Y ₃ and Y ₄ are the same or different hydrogen atoms, halogen atoms, alkyl groups or haloalkyl groups, and P ₁ , P ₂ , P ₃ and P ₄ are the same or different 1 to 5, M is an alkali metal.) A cyclic polyether composition mainly consisting of an organoboron compound represented by: