JPH04339251A - Potassium ion selective composition - Google Patents

Abstract

PURPOSE:To realize a composition having the high reversible catching capacity of a potassium ion by forming said composition from a specific calix arene compound and a thermoplastic resin. CONSTITUTION:A potassium ion selective composition is formed by compounding 0.1-20 pts.wt. of a calix arene compound represented by formula I [wherein X is -CH2-(-CH2OCH2-)n-CH2-, n is 3 or 4, R is a substituted or non-substituted lower alkyl group or an acyl group and R1 is a 4-18C alkyl group, an aryl group or a cycloalkyl group] with 100 pts.wt. of a thermoplastic resin. Since this composition has the reversible catching capacity of a potassium ion, the coordination and dissociation of an ion are extremely good and the film formed from the composition can be utilized as the electrode film constituting a potassium electrode.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a calixarene composition comprising a calixarene compound having a crosslinked structure and a thermoplastic resin, and particularly exhibiting a reversible scavenging ability for potassium ions.

0002

BACKGROUND OF THE INVENTION Conventionally, compounds having a reversible scavenging ability for potassium ions have been required for purposes such as separation and analysis of potassium ions. Antibiotics such as valinomycin and cyclic polyether compounds are known as representative compounds, and the film-like material obtained by molding a composition containing these compounds is being considered for application as a potassium-selective electrode. has been done. Valinomycin exhibits extremely high potassium selectivity, but it is not only extremely expensive and uneconomical as it is extracted from actinomycetes in minute amounts, but also is unstable to heat and cannot be stored frozen because it is a polypeptide compound. However, it had drawbacks such as the fact that it required extreme care in handling. Regarding cyclic polyether compounds, the performance of cryptand and crown ether compounds has been investigated. Regarding cryptand compounds, it is known that [2,2,2]cryptand in particular has high selectivity for potassium ions, but cryptand does not easily dissociate ions once incorporated, so it is not suitable as an electrode compound. Not yet. Furthermore, although it is known that there are crown ether compounds that exhibit potassium selectivity, no compound that has selectivity equivalent to valinomycin has yet been obtained.

0003

[Problems to be Solved by the Invention] As a result of repeated research to develop a new composition that has a high ability to reversibly scavenge potassium ions, the present inventors found that a specific calixarene compound and a thermoplastic resin The present inventors have discovered that a composition consisting of the following has the above characteristics and is a particularly useful material as a potassium electrode, and has come to propose the present invention.

0004

[Means for Solving the Problems] That is, the present invention provides 100 parts by weight of a thermoplastic resin and the following general formula (1).

0005
]

[Case 2]

[In the formula, X is -CH2-(-CH20CH
2-) n-CH2-{n is an integer of 3 or 4}, R is a substituted or unsubstituted lower alkyl group or acyl group, R
1 represents an alkyl group, an aryl group, or a cycloalkyl group having 4 to 18 carbon atoms] 0.1 to 20 parts by weight of a calixarene compound. .

R1 in the above general formula (1) is a t-butyl group, a 1,1,3,3-tetramethylbutyl group (hereinafter referred to as
A linear or branched alkyl group having 4 to 18 carbon atoms such as a t-octyl group, an n-octyl group, or an n-octadecyl group, an aryl group such as a phenyl group, or a cycloalkyl group such as a cyclohexyl group is used.

In the above general formula (1), when R is an unsubstituted lower alkyl group, specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, etc. .

In addition, in the above general formula (1), when R is a lower alkyl group having a substituent, the group is represented by the following general formula (2).
It is expressed as

-(-CH2-)m-R2
(2) [m is an integer of 1 or 2. R2 represents a halogen atom, a cyano group, a hydroxyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an N,N-dialkylcarbamoyl group, an alkylcarbonyloxy group, an alkoxycarbonyloxy group] A lower alkyl group having any of these substituents; Specific examples include halogenomethyl and halogenoethyl groups such as chloromethyl, bromomethyl and chloroethyl groups; cyanomethyl and cyanoethyl groups; hydroxymethyl and hydroxyethyl groups; alkoxy groups such as methoxyethyl and ethoxyethyl groups; Methyl groups and alkoxyethyl groups; alkylcarbonylmethyl groups and alkylcarbonylethyl groups such as butylcarbonylmethyl groups and ethylcarbonylethyl groups; alkoxycarbonylmethyl groups and alkoxycarbonylethyl groups such as ethoxycarbonylmethyl groups and propyloxycarbonylethyl groups; N,N-dialkylcarbamoylmethyl groups and N,N-dialkylcarbamoylethyl groups such as N,N-dimethylcarbamoylmethyl group, N-butyl-N-isopropylcarbamoylethyl group; propylcarbonyloxymethyl group, butylcarbonyloxyethyl group Examples include alkylcarbonyloxymethyl groups and alkylcarbonyloxyethyl groups such as; alkoxycarbonyloxymethyl groups and alkylcarbonyloxyethyl groups such as methoxycarbonyloxyethyl group and ethoxycarbonyloxyethyl group;

Further, in the above general formula (1), when R is an acyl group, specific examples thereof include an acetyl group, a propionyl group, a butyryl group, and the like.

In the above general formula (1), when R is an unsubstituted lower alkyl group, it is particularly preferable from the viewpoint of selectivity that R is an ethyl group and X is n=3.

Some of the compounds represented by the general formula (1) of the present invention are known [J. Am. Chem. Soc. ，
vol. 112, p6979 (1990)], but also includes new compounds. Usually, the identity of the compound can be confirmed by the following measurements.

(1) Infrared absorption spectrum Absorption derived from ether bonds is 1240-1280, 1000-12
It appears strongly at 00cm￣1. 1720 to 1770c when having a carbonyl group or a hydroxyl group, respectively
It exhibits absorption at m-1, 3200-3550 cm-1.

(2) Proton Nuclear Magnetic Resonance Spectrum Calix[4]arene, in which benzene rings are linked with a methylene group that is free to rotate, can have conformational isomers. When synthesizing a calix[4]arene compound having substituents on all hydroxyl groups,
Since the orientation of the benzene ring is fixed and the degree of conformational freedom is reduced, multiple isomers of the four conformationally derived structural isomers that are stable at room temperature may be generated. In proton nuclear magnetic resonance spectra, the spectral patterns of methylene protons and aromatic protons between benzene rings are characteristic for each conformation [Tetrahedron, vol. 43, p49
17 (1987)].

When measured with reference to tetramethylsilane in deuterated chloroform solvent, the main signal was 8.2
〜6.5ppm Aromatic proton 4.5〜
3.0 Methylene proton at benzyl position 4.5-1.5 Ether site (-C
H2-O-) protons 2.0 to -0.5 Methyl, methylene,
This is shown in the protons of alkyl groups such as methine. Furthermore, when the following substituent is present, the signal of hydrogen attached to the adjacent carbon of the substituent is shown at the following position.

6.0-4.5ppm Halogen atom 5.0-2.0 Nitrogen atom of amino group, amide group 5.0-1.5 Carbonyl group
The relative intensity ratio of these peaks, respectively, is expressed by the general formula (
This corresponds to the ratio of the number of protons bonded to each group calculated from the compound of 1).

(3) Molecular weight measurement By measuring by vapor pressure osmotic pressure method (VPO method),
Obtain a value close to the theoretical molecular weight.

(4) Elemental Analysis The theoretical amounts of carbon, hydrogen, and nitrogen calculated from the compound of the general formula (1) almost match the amounts of each element as determined by the analysis. Typical properties of the calixarene compound represented by the above general formula (1) are as follows.

a. In the usual production method, it is obtained as a white solid, colorless needle crystals, or colorless plate crystals at room temperature (25°C).

b. Solubility is determined by substituent R in general formula (1),
Although it varies slightly depending on R1, it dissolves in methylene chloride, chloroform, tetrahydrofuran, N,N-dimethylformamide, 1,2 dichloroethane, benzene, toluene, ethyl acetate, dioxane, and hexane at room temperature. Dissolves in methanol, ethanol, isopropyl alcohol, etc. under heating. Also, it hardly dissolves in water.

The method for producing the calixarene compound represented by the general formula (1) of the present invention is not particularly limited, and any method may be employed. Industrially suitable two-step synthesis methods are shown in (i) and (ii).

(i) Synthesis method via a precursor having a crosslinked oxyethylene chain represented by the following general formula (3)

0024
]

[Chemical formula 3]

[In the formula, the definition of X and R1 is the general formula (1
)] The raw p-tetraalkyl-substituted tetrahydroxycalix[4]arene compound represented by the following general formula (4) is described in the review [Calixarenes, p216-219,
C. David Gutsche (Royal So
It is a known compound described in the Society of Chemistry).

[0026]

[C4]

[In the formula, the definition of R1 is the same as in general formula (1)] The compound and the compound Z represented by the following general formula (5)
-CH2-(-CH2OCH2-)n-CH2-Z
(5) [where n is an integer of 3 or 4, Z is a halogen atom such as chlorine, bromine, iodine, or a methanesulfonyl group, p
- a group selected from organic sulfonyl groups such as toluenesulfonyl group and brosyl group] in a solvent, a calixarene precursor represented by the general formula (3) can be obtained.

As the base, metal hydrides, metals, metal hydroxides, metal alkoxides, metal carbonates, etc. are used. Examples of the metal hydride include compounds containing alkali metals and alkaline earth metals such as lithium hydride, sodium hydride, potassium hydride, and calcium hydride, but sodium hydride is preferably used. The metal hydroxide is not particularly limited as long as it contains an alkali metal or alkaline earth metal, but sodium hydroxide, potassium hydroxide, cesium hydroxide, and barium hydroxide are preferably used. As the metal, an alkali metal such as lithium, sodium, potassium, etc. is used. As the metal alkoxide, a compound containing an alkali metal such as sodium methoxide, potassium t-butoxide, and phenyllithium is used. Any metal carbonate containing an alkali metal or alkaline earth metal is sufficient, but it is preferable to use sodium bicarbonate, potassium bicarbonate, barium bicarbonate, sodium bicarbonate, or potassium bicarbonate.

The molar ratio of the raw materials to be used can be selected within a wide range, but usually the compound of general formula (5) is in a range of 0.1 to 4 times that of the compound of general formula (4), or even in the vicinity of equimolar amounts. It is preferable that there be. The solvent used can be used without any restriction as long as it is inert to the raw materials. For example, aliphatic hydrocarbons such as hexane, heptane; benzene, toluene,
Aromatic hydrocarbons such as xylene; ethers such as tetrahydrofuran, diethyl ether, and dioxane; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; amides such as formamide, N,N-dimethylformamide, and N,N-dimethylacetamide Nitriles such as acetonitrile, etc. can be used as a single solvent or in a mixture of two to three types of solvents as necessary. When a metal hydride is used, ethers such as tetrahydrofuran and amides such as N,N-dimethylformamide are preferably used as reaction solvents. Although the reaction temperature is not particularly limited, a range of 0 to 150°C is generally suitable. The reaction time is also not particularly limited, but is generally 1~
100 hours is sufficient.

[0030] The precursor of general formula (3) obtained by the above method and the compound R-Z represented by the following general formula (6)
(6) [wherein R is Z of general formula (1)
is the same as the definition of general formula (5)] and a base in a solvent to obtain a calixarene compound represented by general formula (1).

As reaction conditions, the base, reaction solvent, reaction temperature and reaction time employed in the reaction to obtain the precursor of general formula (3) are preferably used. The molar ratio of the raw materials used can be selected within a wide range, but usually the amount of the compound of general formula (6) is in the range of 0.5 to 8 times, or even twice the amount of the precursor of general formula (3). is preferred.

(ii) Synthesis method via a precursor represented by the following general formula (7)

[0033]

[C5]

[The definitions of R and R1 are the same as in general formula (1)] By reacting the compounds represented by the above general formulas (4) and (6) with a base in a solvent, the above general formula A calixarene precursor represented by (7) is obtained. As reaction conditions, the base, reaction solvent, reaction temperature and reaction time employed in the reaction to obtain the precursor of general formula (3) are preferably used. The molar ratio of the raw materials used can be selected within a wide range, but usually the amount of the compound of general formula (6) is in the range of 0.5 to 8 times, or even twice the amount of the compound of general formula (4). preferable.

The calixarene compound of the general formula (1) is obtained by reacting the precursor of the general formula (7) obtained by the above method and the compound of the general formula (5) with a base in a solvent. . As the reaction conditions, the synthesis conditions of the precursor of general formula (3) are similarly adopted. The molar ratio of the raw materials to be used can be selected within a wide range, but usually the compound of general formula (5) is in a range of 0.5 to 8 times that of the precursor of general formula (7), or even in equimolar amounts. is preferred.

The calixarene compounds and calixarene precursors represented by general formulas (1), (3) and (7) are purified by extraction, recrystallization and column chromatography. In particular, column chromatography is preferably used to separate precursors and purified isomers. When employing this method, it is necessary to consider in advance the optimal conditions for the column packing material and developing solvent in thin layer chromatography.

One of the necessary components of the potassium selective composition containing the calixarene compound 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 calixarene composition of the present invention is formed into a film 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 homopolymers or copolymers of vinyl halides such as vinyl chloride, vinyl bromide, vinylidene chloride, and tetrafluoroethylene; styrene;
Homopolymers or copolymers of styrene and its substituted products such as chlorostyrene and bromostyrene; homopolymers of acrylic esters such as methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl methacrylate, or methacrylic esters Coalescing or copolymers; homopolymers or copolymers of vinyl esters such as vinyl acetate; diene polymers such as butadiene and isoprene, or copolymers of these dienes with styrene, alrylonitrile, etc.; polyurethanes; siloxanes Polymers or copolymers; examples include cellulose compounds such as cellulose acetate and cellulose nitrate.

The calixarene composition of the present invention is a composition containing a calixarene compound represented by general formula (1) and a thermoplastic resin. The blending ratio of the calixarene compound is not particularly limited as long as it exhibits the desired performance, but it is generally 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the thermoplastic resin. It is suitable to use within the range of . If the amount of the calixarene compound is less than 0.1 part by weight, the selectivity for potassium ions tends to decrease, and this may be undesirable as a composition constituting a potassium electrode. Also,
If the amount is more than 20 parts by weight, the calixarene compound tends to precipitate, and in extreme cases, layer separation occurs between the calixarene compound layer and the thermoplastic resin layer, resulting in non-uniform calixarene composition. This is generally not desirable as it may cause

Even when the calixarene composition of the present invention is composed of the above-described calixarene compound and a thermoplastic resin, it is possible to construct a potassium electrode that can be fully used in practical use, as shown in the examples. , further an organic boron compound represented by the following general formula (8)

[0040]

[C6]

[In the formula, Y1, Y2, Y3, and Y4 are the same or different hydrogen atoms, halogen atoms, alkyl groups, or haloalkyl groups, and h, i, j, and k are the same or different integers of 1 to 5. , M represents an alkali metal] in a molar ratio of 0.001 to 1 to the calixarene compound.
．． By using the composition preferably in the range of 0.01 to 0.8, when the composition of the present invention is used as a potassium electrode, the measurement sensitivity can be improved. If the amount of the organic boron compound exceeds 1.0 (molar ratio), when the calixarene composition of the present invention is used as a potassium electrode, selectivity and sensitivity for potassium ions may be significantly reduced, so it is preferable. do not have.

In the general formula (8), fluorine, chlorine, bromine, or iodine atoms are used as the halogen atoms represented by Y1, Y2, Y3, and Y4. In addition, in the general formula (8), the alkyl groups represented by Y1, Y2, Y3, and Y4 are not limited to the number of carbon atoms, but
Generally, those having 1 to 4 carbon atoms are preferred. in particular,
Examples include methyl group, ethyl group, n-propyl group, n-butyl group, and the like. Furthermore, as the haloalkyl group, those in which at least one or more hydrogen atoms of the above-mentioned alkyl groups are substituted with a halogen atom can be used without any limitation. Specifically, fluoromethyl group, chloromethyl group, bromoethyl group, iodopropyl group, chlorobutyl group, dichloroethyl group, dibromopropyl group, trifluoromethyl group, trichloromethyl group, tribromopropyl group, pentafluoroethyl group, etc.

The organic boron compound represented by the general formula (8) used in the present invention can be prepared by a known method, for example, [I
．． Prackt. Chem. , vol. 26, p1
5 (1964)] and [Synth. React.
Inorg. Met. -Org. Chem. , vol.
．． 10, p. 261 (1980)]. Among the organic boron compounds represented by the general formula (8), compounds in which Y1, Y2, Y3, and Y4 are a hydrogen atom, a fluorine atom, a chlorine atom, or a trifluoromethyl group are easily available, or It is preferably used in the present invention because it can be easily derived from the available material by salt exchange to the desired alkali metal salt. Further, in the general formula (8), potassium, rubidium, cesium, etc. are preferable because they generally have low solubility in water, and potassium is particularly preferable. When the alkali metal is lithium or sodium, they generally have high water solubility.
Depending on the combination with the calixarene compound shown in 1), the resulting composition may not be suitable for the intended use.

[0044] Since the calixarene composition of the present invention contains a thermoplastic resin, it can be formed into any shape depending on the purpose, such as a film-like material, a granular material, a fibrous material, etc. When formed into a film-like material, it can be applied as a potassium electrode, and when formed into a granular or fibrous material, it can be applied to an ion adsorption resin or a chromatography material.

[0045] The case where the calixarene composition of the present invention is formed into a film-like product will be explained below.

When the film-like material obtained by molding the calixarene composition of the present invention is used as a film-like material constituting a potassium electrode, the thickness of the film-like material is not particularly limited; It is sufficient to select it within the range of 1 to 1000 μm. In addition, it is better for the above-mentioned film-like material to have flexibility, and generally the tensile modulus (25°C) of the film-like material is 1 to 1.
A material having a weight in the range of 200 kg/cm2 is preferably used. When polyurethanes and polysiloxanes are used as thermoplastic resins, these resins can be used as they are, but thermoplastic resins that give a film-like material that is relatively lacking in flexibility, such as polyvinyl chloride and polystyrene, etc. When using plasticizers, it is best to use plasticizers. The plasticizer is not particularly limited and any known plasticizer may be used, but in general, the following may be used. For example, phthalate esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, and dioctyl phthalate; fatty acid esters such as dioctyl adipate and dioctyl sebacate; O-nitrophenyl phenyl ether,
- Diphenyl ethers such as fluoro O' nitrodiphenyl ether; O-nitrophenyl alkyl ethers such as O-nitrophenyl octyl ether. The amount of these plasticizers added may be appropriately selected depending on the purpose of use of the film-like material, but in general, the amount of thermoplastic resin 10
It is preferable to select the amount of plasticizer in the range of 30 to 300 parts by weight relative to 0 parts by weight.

[0047] The method for producing the above film-like material is not particularly limited. Typical manufacturing methods that are generally suitably employed are as follows.

■ The calixarene compound represented by the general formula (1) is dissolved in an organic solvent together with a thermoplastic resin or with the addition of a plasticizer, and the solution is applied or poured onto the top surface of the plate, and then A method of evaporating an organic solvent to form a film. As the organic solvent, any known organic solvent can be used without any restriction as long as it dissolves the thermoplastic resin and the calixarene compound. Specific examples of generally suitably used organic solvents include tetrahydrofuran, dioxane, dimethylformamide, dimethylacetamide, chloroform, 1,2-dichloroethane, methylene chloride, methyl ethyl ketone, cyclohexanone, benzene, and toluene.

Furthermore, when adding an organic boron compound represented by the general formula (8), even if the organic boron compound alone is poorly soluble in an organic solvent, if a calixarene compound is present, the molar amount relative to the compound is 0.5 in ratio
Since solubilization is often involved in the following, it is desirable to conduct a dissolution test in advance before selecting a solvent.

■ A calixarene compound is added to a thermoplastic resin, a plasticizer, and, if necessary, an organic boron compound represented by the general formula (8),
There is a method of heating and forming the mixture as a raw material to form a film-like product. The heating and refluxing method is not particularly limited, and any known method can be employed. For example, a method in which a calixarene compound and a thermoplastic resin, or a mixture to which a plasticizer is added if necessary, is melted and extruded at a temperature higher than the softening temperature or melting temperature of the thermoplastic resin and formed into a film, or the mixture is heated. What is necessary is just to adopt the method of forming into a film-like object by a press.

The film-like material obtained by the method described above is particularly suitable for use as a potassium electrode. With regard to the aspect of constructing the membrane-like material into a potassium electrode, known methods can be used without particular limitation. For example, a solution containing the composition of the present invention obtained by the method (1) above is poured onto a glass plate, and then the solvent is removed to form a film-like material. Potassium electrodes can be made by cutting them into a predetermined size and attaching a membrane to a membrane holder to form a potassium electrode, or by forming a thin film directly on the surface of a silver wire, platinum, etc., or on the gate of a silicon semiconductor. Examples include a method of using it as an electrode.

[0052]

[Examples] Examples are given below to explain the present invention more specifically, but the present invention is not limited to these Examples.

Example 1 100ml of dry benzene was added and a cooling tube was attached.
Put pt-octyltetrahydroxycalix[4]arene 2. into a 00ml three-necked flask under a nitrogen atmosphere.
Add 0 mmol and 2.0 mmol of t-BuOK to 1
Stir for an hour. 1.0 mmol of tetraethylene glycol di-p-toluenesulfonate is added and the reaction solution is heated to reflux. After 4 hours, 1.0 mmol of tetraethylene glycol di-p-toluene sulfonate was added.
Heating and refluxing was continued for 0 hours. After cooling, the reaction mixture was poured into a 1N aqueous hydrochloric acid solution containing ice, the organic layer was separated, and the aqueous layer was extracted twice with diethyl ether. The organic layers were combined and washed twice with water. After drying the organic layer, the resulting residue was recrystallized from methanol to obtain the crosslinked compound shown below.
6 mmol (yield 30%) was obtained.

[0054]

[C7]

[In the formula, X is -CH2-(-CH20CH
2-)3-CH2-] Dissolve 1.5 mmol of the crosslinked compound obtained in the above reaction in 40 ml of dry tetrahydrofuran and 8 ml of dry dimethylformamide in a 100 ml eggplant-shaped flask, add sodium hydride, and add ethyl bromide 3. .6 mmo
1 was added. The reaction mixture was heated to reflux under nitrogen atmosphere for 4 hours. The reaction mixture was concentrated under reduced pressure, and the residue was 0.5
The mixture was poured into an aqueous solution of N hydrochloric acid, and the aqueous layer was extracted three times from chloroform. The organic layers were combined and washed twice with water. After drying the organic layer, the resulting residue was subjected to silica gel column chromatography (silica; Wakogel C-200, developing solvent: chloroform), followed by thin layer chromatography (by recrystallizing from methanol). Silica-chloroform), the compound showing Rf=0.45 was
．． Obtained 33 g as colorless needles.

[0056] The analysis results of the obtained compound are shown below.

(1) Infrared absorption spectrum 1185cm-1 Ar-O-C1092
C-O-C(2) proton nuclear magnetic resonance spectrum 7.2-6.8 ppm m4.4
d4.0-3.4
m3.2
d1.5-1.0 m Furthermore, the ratio of hydrogen amounts obtained by integration matched that of the target product.

[0058] From the analysis results and proton nuclear magnetic resonance spectrum, it was confirmed that the following compound had a partial-cone conformation. Later Example 20
, 22, the compound was converted into Compound No. It is called 1.

[0059]

[Chemical formula 8]

[In the formula, X is -CH2-(-CH20CH
2-) 3-CH2-, R is ethyl group] In addition to the above compound, 0.12 g of a component with Rf=0.76 was added by thin layer chromatography (silica-chloroform), and Rf=0.
0.48g of component 14 was obtained. As a result of analysis, these compounds are conformational isomers of the compound shown by the above structural formula, and the component with Rf = 0.76 is 1,3-al
ternate conformation, Rf=0.14
It was confirmed that the component has a cone conformation.

Examples 2 to 14 Calixarene compounds represented by the general formula (1) were synthesized in the same manner as in Example 1, and compounds having the structures shown in Table 1 were synthesized. Table 1 shows the obtained compound, its conformation, and yield.

[0062]

[Table 1]

The compounds synthesized in Examples 2 to 14 were confirmed to be the target compounds in the same manner as in the Examples. Identification data are shown in Table 2.

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

[Table 4]

[0067]

[Table 5]

Example 15 Into a 200 ml eggplant-shaped flask containing 70 ml of dry acetonitrile, 1.5 mmol of p-n dodecadecyltetrahydroxycalix[4]arene, 30 mmol of potassium carbonate, and 3.0 mmol of isopropyl-p-toluenesulfonate. was added and heated under reflux for 22 hours under nitrogen atmosphere. After distilling off the solvent under reduced pressure, the residue was boiled in 4N potassium hydroxide for 2 hours. After cooling to room temperature, the solid matter was filtered off and the resulting crude product was recrystallized from ethanol:chloroform to obtain 1.1 mmol (yield 73%) of a calixarene compound.

[0069]

[Chemical formula 9]

[In the formula, R is an isopropyl group] 1.0 mmol of the calixarene compound obtained in the pre-reaction and 2.2 mmol of metallic potassium were added to a 200 ml three-necked flask equipped with a condenser tube containing 60 ml of dry toluene. The mixture was heated under reflux for 1 hour under a nitrogen atmosphere. Tetraethylene glycol dibromide was added, and heating and refluxing was continued for an additional 20 hours. After cooling the reaction mixture, it was poured into a 0.5N aqueous hydrochloric acid solution. After separating the organic layer, the aqueous layer was extracted three times with chloroform. After drying the organic layer, the residue was subjected to column chromatography (stationary phase: alumina gel, developing solvent: ethyl acetate:hexane = 9:1), and then extracted with chloroform. :Methanol=1:4 to obtain 0.67 g of colorless plate crystals.

The following analysis was performed on the obtained compound.

(1) Infrared absorption spectrum 1192 cm-1 Ar-O-C1085
C-O-C(2) proton nuclear magnetic resonance spectrum 7.2-6.8 ppm m 4.3 d4
．． 1-3.4 m3.2
d2.3
t1.5~1.1
m-0.1
dAlso, the ratio of hydrogen amounts obtained by integration matched that of the target product.

[0073] From the analysis results, it was confirmed that the following compound had a partial-cone conformation. In later Examples 20 and 22, this compound was replaced with compound N
o. It is called 2.

[0074]

[Chemical formula 10]

[In the formula, X is -CH2-(-CH20CH
2-) 3-CH2-, R is isopropyl group] Examples 16 to 19 A calixarene compound represented by the general formula (1) was synthesized in the same manner as in Example 15, and the structure shown in Table 3 was synthesized. The compound was synthesized. The obtained compounds, their conformations, and yields are shown in Table 3.

[0076]

[Table 6]

The compounds synthesized in Examples 16 to 19 were confirmed to be the target compounds in the same manner as in Example 15. Identification data are shown in Table 4.

[0078]

[Table 7]

An example of application of the composition of the present invention to a potassium selective electrode will be shown below.

Example 20 Obtained in Examples 1 to 19,
The compounds of the present invention shown in Tables 1 and 3 and the known compounds shown in Table 5 [J. Am. Chem. Soc. , vol.
112, p6979 (1990)] at 10 m
g, polyvinyl chloride (degree of polymerization 1100) 200 mg, O
- 400 mg of nitrophenyl octyl ether in 10 m
1 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 attached to an electrode as shown in FIG. 2, and the electrode performance was evaluated using the apparatus shown in FIG. All measurements were performed at 25°C. The performance of electrodes constructed using these membrane materials is shown in Table 6.

[0081]

[Table 8]

[0082]

[Table 9]

The selectivity of potassium ions over sodium ions was determined based on the mixed solution method described in Chapter 2, Section 3 of "Ion Selective Electrodes" (Kyoritsu Shuppan 1977). Specifically, in a solution containing potassium chloride and sodium chloride, potassium chloride was added to a constant concentration (10￣
4M), and the electromotive force was measured while changing the concentration of sodium chloride. Then, the relationship between the electromotive force and the 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 is, the better the electrode is as a potassium selective electrode.

[0084] Also, only potassium chloride was added at a concentration of 10-1 to 10
- From the relationship between the electromotive force and potassium chloride concentration of an aqueous solution in the concentration range of 4M, the slope is expressed as the amount of change in electromotive force when the potassium chloride concentration changes 10 times (mV/deca).
It was determined in units of de.

Example 21 10 mg of the calixarene compound shown in Tables 1, 3 and 5, a thermoplastic resin and a plasticizer having the composition shown in Table 7 were dissolved in 10 ml of tetrahydrofuran. After this solution was cast on a smooth glass plate, the tetrahydrofuran was evaporated to obtain a film with a thickness of about 100 μm. The performance of electrodes constructed using these membrane materials is shown in Table 7. In Table 7, thermoplastic resins and plasticizers are abbreviated as follows.

[0086] Polyvinyl chloride
:PVC polymethyl methacrylate
:PMMA polystyrene
:PSt Polyvinylidene chloride :PVD
CO-nitrophenyl octyl ether:
NPOE dibutyl phthalate
:DBP dioctyl phthalate
:DOP dioctyl adipate :DO
AO-nitrophenylphenyl ether:
NPPEO-Fluoro O'nitrodiphenyl ether: FNDPE

[0087]

[Table 10]

Example 22 20 mg of the calixarene compound shown in Table 8, 200 mg of the thermoplastic resin, 300 mg of the plasticizer and the general formula (8
) in 1,2-dichloroethane at a predetermined molar ratio to the calixarene compound.
After dissolving the solution in 0 ml, it was cast onto a glass plate, and 1,2-dichloroethane was evaporated to obtain a film with a thickness of about 100 μm. Table 8 shows the electrode performance of the potassium electrode constructed using the obtained film-like material.

As shown in Table 8, the addition of the organic boron compound shows an extremely high slope of 57 to 60 mV, and it is clear that a highly sensitive potassium electrode can be constructed.

[0090]

[Table 11]

[0091]

[Table 12]

[0092]

[Table 13]

[0093]

[Effect of the invention] The calixarene composition of the present invention has
As mentioned above, since it has a reversible scavenging ability for potassium ions, the absorption and dissociation of these ions is extremely good, and the film-like material formed from this can be used as an electrode film constituting a potassium electrode. can.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram of an apparatus for measuring electromotive force.

2 is an explanatory diagram showing various constituent elements built into the electrode 1 of FIG. 1. FIG.

[Explanation of symbols]

1 Electrode 2 Measuring solution 3 Magnetic stirrer 4 Magnetic stirrer 5 1M lithium acetate salt bridge 6 Potassium chloride saturated solution 7 Saturated liquid electrode 8 Electrometer (Hokuto HE-103 type) 11
Acrylic membrane holder 12 Silver wire 13 Covered glass tube 14 Silver-silver chloride internal standard electrode 15 10￣2M potassium chloride internal standard solution 16 Membrane containing calixarene compound 17 o -
ring

Claims (1)

[Claims] Claim 1: 100 parts by weight of a thermoplastic resin, and the following general formula (1) [wherein, X is -CH2-(-CH20CH2-)n-C]
H2-{n is an integer of 3 or 4}, R is a substituted or unsubstituted lower alkyl group or acyl group, R1 has 4 carbon atoms
~18 alkyl group, aryl group or cycloalkyl group] Calixarene compound represented by 0.1
-20 parts by weight of a potassium ion selective composition.