JP3016522B2 - Composite molecular alignment film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite molecular alignment film which can be suitably used for an anion-sensitive film used for an ion-selective electrode for analyzing ions in a solution.

[0002]

2. Description of the Related Art In medical treatment, it is common to measure sodium ions, potassium ions, and chloride ions in blood and urine, and use them for diagnosis. The specific ion concentration in biological fluids is closely related to the metabolic mechanism of living organisms,
From these ion concentrations, various diagnoses such as hypertension, heart disease, and neuropathy are made. In recent years, it has become common to use ion-selective electrodes for measuring these ions.

Generally, as shown in FIG. 1, an ion-selective electrode is an electrode cylinder 1 provided with an ion-sensitive membrane 12 as a boundary film at a portion (generally, a bottom) immersed in a sample solution.
1 is basically constituted by providing an internal electrolyte 13 and an internal reference electrode 14.

FIG. 2 shows a typical structure of an ion measuring device for measuring the activity of ions in a solution using such an ion selective electrode. That is, the ion selective electrode 21 is immersed in the sample solution 23 together with the salt bridge 22, and the other end of the salt bridge is immersed in the saturated potassium chloride solution 26 together with the reference electrode 24. The potential difference between the two electrodes is read by the electrometer 25, and the ion activity of a specific ion species in the sample solution can be determined from the potential difference.

Conventionally, various films have been proposed as anion-sensitive films for selectively detecting anions, particularly chloride ions. When a bromide ion, cyanide ion, thiocyanate ion, etc. are present in a solution, a solid film mainly composed of silver chloride causes a chemical change on the film surface due to the influence of these ions. May not be able to measure potential. Further, in measurement of various biological fluids and the like, there is a disadvantage that the protein is easily affected by the protein and the like, and the electric potential is still unstable. In addition, a polymer membrane using a quaternary ammonium salt as an ion-sensitive substance is also used, but the influence of anions other than chloride ions, for example, phosphate ions, hydrogen carbonate ions, etc. is large, and accurate measurement cannot be performed. It has the disadvantage that it may be.

In recent years, an anion-sensitive membrane in which a crown ether compound is polymerized and a cation is immobilized in the membrane has been proposed (L. Angele, J. Simonet: New Journal of C.).
hemistry, vol. 14, 83-86 pages (1990)). Crown ether has a high ability to form a complex with a cation, the cation is immobilized in the membrane, and the membrane itself is considered to be an anion-sensitive membrane. Although this film shows a potential response to anions, it has drawbacks such as lack of mechanical strength due to being a thin film, lack of durability, and a complicated film forming method for forming anion-sensitive films. Was.

[0007]

Accordingly, there has been a demand for the development of an anion-sensitive membrane which provides an ion-selective electrode capable of measuring chlorine ions in a biological fluid with high sensitivity and stability.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to develop an anion-sensitive film capable of solving such a problem. As a result, a composite molecular alignment film composed of a polymer having a specific structure and a specific compound having a cation-capturing ability has excellent ion sensitivity to chloride ions, and has good water resistance. As a result, the present inventors have found that an ion-selective electrode capable of measuring chlorine ions with high sensitivity and stability can be obtained by using as an anion-sensitive membrane. Conventionally, an anion-sensitive membrane in which an anion-sensitive substance comprising a quaternary ammonium salt is dispersed in a carrier such as a polymer has been known, but an anion in which a compound having a cation-capturing ability is dispersed in the carrier is known. No sensitive membrane is known.

That is, the present invention relates to (A) a general formula [1] Ｘ In the formula, X is a nonionic monovalent group having 1 carbon atom
A linear hydrophobic group of 0 to 30 composed of one or two or at least two aromatic rings connected via a direct bond, a carbon-carbon multiple bond, a carbon-nitrogen multiple bond, an ester bond or an amide bond Having any one of a straight-chain hydrophobic group having 4 to 30 carbon atoms containing a divalent group in the chain, Y is

[0010]

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Wherein R ³ is hydrogen or methyl, R ² is —CO—, —COO—, —O— and —
A divalent group selected from CONH-, n is an integer of 1 to 4,
m represents an integer of 1 or 2), and R ¹ represents a group selected from hydrogen, a methyl group, a cyano group, and a halogen atom. And (B) general formula [2]

[0012]

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Where i is an integer from 4 to 8, and T is

[0014]

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And U represents a group selected from

[0016]

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Represents a group selected from the group consisting of:

[0018]

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Represents a group selected from the group consisting of

[0020]

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A composite molecular orientation film comprising a calixarene compound represented by｝ which represents a group selected from the group consisting of: and a negative ion sensitive film comprising the orientation film. In the present invention, in the general formula [1], X represents one or two linear hydrophobic groups having 10 to 30 carbon atoms, a direct bond, a carbon-carbon multiple bond, a carbon-nitrogen multiple bond, an ester bond or an amide. A nonionic monovalent having any one of a linear hydrophobic group having 4 to 30 carbon atoms and having a divalent group composed of at least two aromatic rings connected through a bond in a chain; (Hereinafter abbreviated as a hydrophobic group). In the polymer constituting the composite molecular alignment film of the present invention,
The presence of such a hydrophobic group can improve the selection sensitivity when used as an anion-sensitive membrane and can increase the stability when used in water.

In the present invention, the hydrophobic group is a straight-chain alkyl group having 10 to 30 carbon atoms or its halogen-substituted product because of its ion selectivity when used as an anion-sensitive membrane and the availability of raw materials. It is preferable to include, in addition to the completely linear one, a branched one having a branch of up to two carbon atoms. Preferred examples thereof include dodecyl, tridecyl, tetradecyl,
Examples include a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group.

One embodiment of the hydrophobic group of the present invention is a compound having 10 carbon atoms.
It has one or two linear hydrophobic groups of 30 to 30, and if it has three or more, it is difficult to obtain or synthesize a raw material for polymer production.

As another embodiment of the hydrophobic group of the present invention, a nonionic monovalent group having one of the linear hydrophobic groups having a specific structure shown below or in the chain is provided. No.

A direct bond or a carbon-carbon multiple bond,
2 composed of at least two aromatic rings connected via a carbon-nitrogen multiple bond, an ester bond, an amide bond, or the like.
Valent groups, such groups, for example,

[0026]

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And other divalent groups.

Whether two or more aromatic rings are bonded,
A divalent group, which is a single bond between a plurality of atoms, and whose rotation is energetically restricted, specifically exemplifying such a group,

[0029]

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And other divalent groups.

Wherein the aromatic ring forms a condensation,
When this condensed ring is stacked between multiple molecules, a divalent group whose rotation is sterically constrained to each other, such a group is specifically exemplified by:

[0032]

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And the like.

The carbon number of the linear hydrophobic group having one of the linear hydrophobic groups containing a group having the above specific structure in the chain is determined by the water resistance and raw material when used as an anion-sensitive membrane. Is preferably 4 to 30 from the viewpoint of easy availability.
The number of carbon atoms mentioned here means the number of carbon atoms in the specific structure portion and the portion excluding the bonding portion between the specific structure portion and the linear hydrophobic group. In general, a carbon-carbon bond, an ester bond, or an ether bond is preferably used as the bonding portion between the above-described specific structure and the linear hydrophobic group. The reason that the number of linear hydrophobic groups containing this specific structure in the chain is limited to one is that if the number is two or more, remarkable difficulty occurs during mixing with a polymer and subsequent molding processing, and a complex molecular alignment film is formed. This is because it is often undesirable to have a problem with the stability of the polymer.

The hydrophobic group of the present invention is not particularly limited as long as it satisfies the above conditions, and known groups can be used. Typical examples that are generally preferably used are specifically shown below.

[0036]

[0037]

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(Provided that R ⁵ and R ⁶ are the same or different linear alkyl groups having 12 to 30 carbon atoms or a halogen-substituted product thereof, and D represents-(E) _f- and-(CH ₂ ) _d- ｛
E is -Ph-, -Ph-O-, -Ph-OCO- and-
A group selected from Ph-COO- (wherein, Ph represents a benzene ring and is all bonded at the para position), f is 0 or 1, and d is a positive integer. Represents a group selected from｝, and a and b are positive integers. )

[0039]

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(However, R ⁵ , R ⁶ , D, and a are the same as above, and k is 1 or 2.)

[0041]

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(Where R ⁵ and R ⁶ are the same as above,
d is a positive integer. ^{) R 7 -V-G- [6} ] ( where, R ⁷ is an alkyl group, alkyloxy group, or an alkyloxycarbonyl group or a halogen-substituted derivatives thereof, having 4 to 22 carbon atoms, V is,

[0043]

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Where W is -N = CH-, -N = N-,
-CH = CH-, -NO = N-, -CONH-, -CO
O -, - O -, - CO -, - C (CH 3) 2 -, Ph, and -O-Ph-O- from indicates group selected (Ph represents a benzene ring bonded at the para-position ), J is 0 or 1. Represents a group selected from｝, and G represents — (CH ₂ ) _e —,
And -O- (CH _{2) e} - shows from selected groups. (Where e is a positive integer.)) The above general formula [3],
In [4], [5], and [6], d and e may be positive integers, but generally preferably 1 to 16 from the viewpoint of easy availability of raw materials. In the general formula [3], a and b
Can take any positive integer without any limitation, but is generally preferably 1 to 4 from the viewpoint of easy availability of raw materials. Further, the above general formulas [3], [4], [5] and [6]
In the formula, examples of the halogen atom of the halogen-substituted alkyl group represented by R ⁵ and R ⁶ include fluorine, chlorine, bromine, and iodine atoms.

In the general formula [1], Y is

[0046]

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(R ³ is hydrogen or a methyl group, R ² is —CO
, -COO-, -O- and -CONH-, a divalent group, n is an integer of 1 to 4, and m is an integer of 1 or 2. The presence of these hydrophilic groups can reduce the interference response of ions other than chloride ions when used as an anion-sensitive membrane. M is 1 or 2 from the viewpoints of ease of production, availability of raw materials, and durability in water as an anion-sensitive membrane.
It is desirable that

In the polymer constituting the composite molecular alignment film of the present invention, the units other than the unit represented by the general formula [1] are not particularly limited as long as they form a linear polymer. The unit represented by [7] is suitably used.

[0049] (Where P is hydrogen, a halogen atom, a cyano group, an alkyl group, or a carboxyl group; Q is an alkyl group, a carboxyl group, a phenyl group, a naphthyl group, an alkylcarboxyl group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, It is an aminocarbonyl group, an alkyloxy group, an amino group, or an alkylamino group.) The number of carbon atoms of the unit represented by the general formula [7] determines the availability of raw materials and the film forming property of the obtained polymer. Considering 1
It is preferably 0 or less.

In the linear polymer constituting the composite molecular orientation film of the present invention, the weight fraction of the unit represented by the general formula [1] to the total polymer is preferably 50% by weight or more. When the fraction of the unit is less than 50% by weight, ion selectivity in the case of forming an anion-sensitive membrane may be insufficient, and stability when used in water may be deteriorated. Further, the molecular weight of the linear polymer is not particularly limited, but the number average molecular weight is preferably 5,000 or more. When the number average molecular weight is less than 5000, the film becomes brittle.

The method for producing the linear polymer is not particularly limited, and a known method is employed. Generally, a monomer having a structure represented by the following general formula [8] may be homopolymerized, or two or more monomers may be used. It can be obtained by copolymerizing the above.

[0052]

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The definitions and preferred examples of X, Y and R ¹ are as described above. The monomer represented by the general formula [8] may be polymerized singly. Alternatively, the monomer may be copolymerized with a copolymerizable vinyl monomer to form a linear molecule suitable for the composite molecular alignment film of the present invention. Polymer can be obtained. As the vinyl monomer copolymerizable with the monomer represented by the general formula [8], known monomers can be used without particular limitation. Specific examples of typical compounds generally used preferably include, for example, olefin compounds such as ethylene, propylene and butene; halogen derivatives of olefin compounds such as vinyl chloride and hexafluoropropylene; and aromatic compounds such as styrene and vinylnaphthalene. Vinyl ester compounds such as vinyl acetate; acrylic acid derivatives and methacrylic acid derivatives such as methyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, acrylamide and methacrylamide; unsaturated nitrile compounds such as acrylonitrile; methyl vinyl And vinyl ether compounds such as ether.

The polymerization method for producing the linear polymer may be ionic polymerization or radical polymerization, but it is desirable to carry out the polymerization in the presence of a radical initiator. As for the polymerization operation, a generally known operation is not particularly limited and used.
Solution polymerization is preferably used in view of the uniformity of the obtained polymer and the ease of adjusting the composition ratio of the copolymer. The solvent used in the solution polymerization is not particularly limited as long as the solvent used dissolves the monomer. Generally, water, methanol, ethanol, acetone, benzene, dimethylformamide, dichloromethane, tetrachloromethane, chloroform, tetrahydrofuran, dichloroethane, chlorobenzene and the like are preferably used. The above solvents may be used as a mixture of two or more. The polymerization temperature is preferably from 0 ° C to 150 ° C,
-100 ° C is more preferred.

As a method for isolating the linear polymer, various methods known in the art can be used. In the case of solution polymerization, the reaction mixture is put into a solvent which does not dissolve the produced polymer. Preferred is a reprecipitation method.

The linear polymer produced as described above is generally a colorless, white or pale yellow solid. Although it is hardly soluble in water, it is soluble in organic solvents such as dimethylformamide, chloroform, tetrachloromethane, dichloromethane, tetrachloroethane, and tetrahydrofuran at room temperature to 100 ° C. The content of the unit represented by the general formula [1] in the linear polymer is generally determined by elemental analysis.

The cyclic compound represented by the general formula [2], which is another component of the present invention, is generally called a calixarene compound. In the general formula [2], i determines the size of the ring formed by the benzene ring. Depending on the number of benzene rings in one molecule, these compounds may be called calix [i] arene (i is an integer of 4 to 8). It is known that the calixarene compound represented by the general formula [2] has a strong trapping ability for a specific cation. Since the cation is trapped by the oxygen atom bonded to the benzene ring, the radius of the ion that maximizes the trapping ability is determined by the size of the ring. Therefore, the cation trapping ability is determined by the value of i and the type of cation. For example, it is known that sodium ions are strongly captured when i = 4 and potassium ions are strongly captured when i = 6.

The presence of the calixarene compound in the composite molecular alignment film of the present invention exhibits anion sensitivity. The calixarene compound of the general formula [2]
Since either U or T contains a hydrophobic group represented by X, the affinity with the hydrophobic group in the polymer is improved and the polymer is immobilized in the polymer. Further, the elution of the calixarene compound into water is suppressed by the presence of the hydrophobic group, and when used as an anion-sensitive membrane, the storage stability and the potential stability in water are improved.

The mechanism by which an anion sensitivity is exhibited by the presence of the calixarene compound is not clear, but the cations trapped by the calixurene compound are immobilized in the membrane, resulting in an anion exchange membrane. It is considered that this is because it functions as.

As described above, the composite molecular alignment film of the present invention can impart anion sensitivity by capturing cations.

When the composite molecular alignment film of the present invention is used as an anion-sensitive film, 5 to 40 parts by weight of a calixarene compound represented by the general formula [2] is contained in 100 parts by weight of the linear polymer. Is preferred. . More preferably, the amount is in the range of 10 to 30 parts by weight based on 100 parts by weight of the linear polymer. If the amount of the calixarene compound is less than 5 parts by weight, the sensitivity to chloride ions is deteriorated, and if the amount is more than 40 parts by weight, the obtained film becomes brittle.

As the calixarene compound used in the present invention, the compound represented by the general formula [2] is used without any limitation.
5,11,17,23-tetra-t-butyl-25,26,27,28-tetrakis (octadecyloxycarbonyl) -methoxy-calix [4] arene, 25,26,27,28-tetrakis (octadecyloxycarbonyl) ) -Methoxy-calix [4] arene, 25,26,27,28-tetrakis (octadecyloxycarbonyl) -methoxy-calix [6] arene, 25,26,2
7,28-tetrakis (octadecyloxycarbonyl) -methoxy-calix [8] arene, 5,11,17,23-tetra-
Methoxymethyl-25,26,27,28-tetrakis (ethoxycarbonyl) -methoxy-calix [4] arene, 5,11,1
7,23-tetra-methoxymethyl-25,26,27,28-tetrakis (ethoxycarbonyl) -methoxy-calix [6] arene, 5,11,17,23-tetra-methoxymethyl-25,26,27, 28
-Tetrakis (ethoxycarbonyl) -methoxy-calix [8] arene, 5,11,17,23-tetra-lauryloxymethyl-25,26,27,28-tetrakis (ethoxycarbonyl) -methoxy-calix [4] arene And the like.

The method for producing calixarene represented by the general formula [2] is not particularly limited, and a known method may be employed. D. Gutsch, Calixaren
es "(1989, The Royal Society of Chemistry), Te
trahedron vol.42, p1636, JP-A-61-83156, JP-A-61-291546, Journal of Organic Chemistr
y, vol. 51, p742 (1986), Journal of Organic Chemistr
y, vol. 50, p5802 (1985), Journal of American Chemic
al Society, vol. 110, p6153 (1988), Journal of Chemic
al Society Chemical Communication p388 (1985) and the like.

In general, a cyclic oligomer (p-alkylhydroxycalixarene) obtained by reacting a p-alkylphenol with formaldehyde under alkaline conditions is used as a starting material. As the p-alkylphenol, pt-butylphenol and pt-octylphenol are generally used because of their high production yield and easy availability of raw materials. The alkyl group has 10 carbon atoms.
Above this is not preferred because the yield of cyclic oligomer is significantly reduced due to steric hindrance. The reaction is preferably performed at a temperature of 150 ° C to 300 ° C. If the temperature is low, linear oligomers are mainly formed, and cyclic oligomers cannot be obtained. If the temperature is too high, by-products other than oligomers increase, resulting in a low production yield and the danger of operating the synthesis reaction. Is also increased. As the solvent, diphenyl ether whose boiling point is higher than the reaction temperature is preferably used. This cyclic oligomer is a white powder having a high melting point and is a mixture of tetramers to octamers. From this mixture, tetramers to octamers can be obtained by recrystallization with a solvent such as benzene, toluene, or ethyl acetate, or by column chromatography. The general formula is shown below.

[0065]

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(I represents an integer of 4 to 8, and R ⁸ represents an alkyl group.) Further, hydroxycalixarene represented by the following general formula [9] obtained by removing the alkyl group from this compound is useful for derivatization. Compound. This compound can be obtained by reacting the above-mentioned p-alkyl calixarene with an equivalent amount or more of phenol in a solvent in the presence of a Lewis acid to carry out an alkyl group transfer reaction. Benzene, toluene, and nitrobenzene are preferred examples of the solvent, and aluminum chloride as the Lewis acid,
And boron trifluoride. Although the reaction temperature is not particularly limited as long as it is around room temperature, it is desirable to carry out the reaction at a temperature of 10 ° C or more and 40 ° C or less.

[0067]

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(I represents an integer of 4 to 8.) A general method for introducing a group represented by T in the general formula [2] into the above calixarene compound will be described below. The method for introducing these groups is not limited to the method described below.

The following reactions are all carried out in a solvent.
The solvent can be used without particular limitation as long as it does not participate in the reaction, but toluene, benzene, dimethyl sulfoxide, etc. are preferably used in consideration of the ease of solvent removal after the reaction and the solubility of the raw materials. Used. The optimum reaction temperature varies depending on the reactivity of each compound and the boiling point of the solvent, but is generally in the range of 0 ° C to 100 ° C. These compounds can be separated and purified by column chromatography.

T = —CH ₂ R ⁹ (R ⁹ represents an alkyl group having 1 or more carbon atoms) The hydroxycalixarene of the general formula [9] is reacted with an acid chloride having an alkyl group of R ⁹ to form a phenol group. Esterify. Further, a Fries transfer reaction is carried out by reacting this compound with a large excess of aluminum chloride. Thereafter, it can be obtained by performing Wolf-Kisher reduction using hydrazine.

T = —CH ₂ N (R ⁴ ) ₂ , —CH ₂ NXR
⁴ (R ⁴ is as defined in the general formula [2] and X is as defined in the general formula [1].) The hydroxycalixarene of the general formula [9] is converted to HN (R ⁴ ) or HNXR ^{4 in a} solvent under acidic conditions. And a formaldehyde.

T = —CH ₂ OR ⁴ , —CH ₂ OX The calixarene compound obtained above is reacted with an alkyl iodide in a polar solvent such as dimethyl sulfoxide, and then represented by R ⁴ ONa or XONa. It can be obtained by reacting with a compound.

T = —COOR ⁴ , —COOX The calixarene compound of the general formula [9] is reacted with acetic anhydride in the presence of an acid catalyst to obtain an acetyl form. Sulfuric acid and nitric acid are used as the acid catalyst. Next, acylation is carried out by Friedel-Crafts reaction with acetyl bromide under a Lewis acid catalyst. Dissolve the obtained compound in dimethylformamide,
An aqueous solution containing bromine and sodium hydroxide is added, and the mixture is neutralized with an acid. Then, it is reacted with R ⁴ Z or XZ (Z represents a halogen atom) to obtain a target compound.

T = -CH ₂ CH ₂ NHCOR ^{4 The} calixarene compound obtained above is reacted with an alkyl iodide in a polar solvent such as dimethyl sulfoxide, and then reacted with sodium cyanide to obtain a cyanomethyl compound. An amine compound is obtained by reduction by a hydroboration reaction. This is reacted with an alkyl acid chloride compound represented by R ⁴ COCl to obtain the desired compound.

T = —SO ₃ H The calixarene compound of the general formula [9] can be obtained by heating the compound at 80 ° C. or more in 90% sulfuric acid.

T = -NO ₂ The sulfonated calixarene obtained as described above is introduced into nitric acid at a concentration of 30 to 70% at 10 ° C. or less, and a sulfone group is replaced with a nitro group.

T = -COX The calixarene compound of the general formula [9] is converted to ZCOX (Z
Represents a halogen atom such as a chlorine atom and a bromine atom. ) To esterify the phenol group. Further, the compound can be obtained by reacting this compound with a large excess of aluminum chloride and performing Fries rearrangement.

A method for introducing the substituent T into the calixarene compound of the general formula [9] by the above-mentioned methods and then introducing the substituent U in the general formula [2] into the calixarene compound will be described below.

The following reactions are all carried out in a solvent.
The solvent can be used without particular limitation as long as it does not participate in the reaction, but the solvent can be easily removed after the reaction,
Considering the solubility of the raw materials, toluene, benzene, acetone, ethyl acetate and the like are preferably used. The optimum reaction temperature varies depending on the reactivity of each compound and the boiling point of the solvent, but is generally in the range of 0 ° C to 100 ° C. These compounds can be separated and purified by column chromatography.

[0080] ^{U = -X, -R 4, -COX} , in the presence of a base in a -COR ⁴ in a solvent, the various tetrahydroxy calixarene compound obtained by the method and XZ, R ⁴ Z, Z
It is obtained by reacting with a compound represented by COX or ZCOR ⁴ (Z represents a halogen atom such as a chlorine atom or a bromine atom). The base used is XZ,
In the reaction with R ⁴ Z, an inorganic alkali salt, ZCOX, ZCO
In the reaction with R ⁴ , a tertiary amine compound is suitably used. Specific examples include inorganic alkali salts such as sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, and the like.
Examples of the tertiary amine compound include trimethylamine and triethylamine.

[0081] _{U = -CH 2 COOX, ZCH 2} COOX in the presence of a base with -CH ₂ COOR ⁴ in a solvent, ZCH ₂ CO
It can be obtained by reacting with a compound represented by OR ⁴ (Z is as described above). Also, ZCH ₂ COO
After the reaction with R ^4, it may be used a method of substituting R ⁴ and X by an ester exchange reaction with the compound represented by XOH.

The calixarene compound obtained as described above generally has a melting point in the range of 40 ° C. to 100 ° C., and is a white or pale yellow solid at room temperature. In addition, although it is hardly soluble in water, organic solvents such as dimethylformamide, chloroform, tetrachloromethane, dichloromethane, tetrachloroethane, tetrahydrofuran, etc.
Dissolve at room temperature to 100 ° C.

The method of forming the mixture of the linear polymer and the calixarene compound obtained by the above-mentioned production method into a film-like material is not particularly limited, and any method may be used. The following is an example of a method that is generally preferably used.

The linear polymer and the calixarene compound of the present invention are dissolved in a soluble solvent, cast on a suitable substrate, and then the solvent is removed to obtain a film. The solvent used here is not particularly limited as long as it dissolves the linear polymer and the calixarene compound of the present invention, but the soluble solvent described in the above-mentioned polymer production method is suitably used. In order to remove the solvent, air drying, drying under reduced pressure and the like are generally used without any particular limitation.

Although the thickness of the composite molecular alignment film of the present invention is not particularly limited, it is generally 0.1 μm to 5 mm, preferably 5 μm to 5 mm.
When the thickness is in the range of 100 μm, sufficient film strength can be imparted when used for an anion-sensitive film, which is preferable.

The anion sensitive film of the present invention generally exhibits liquid crystallinity as its basic property in many cases. The temperature range showing the liquid crystallinity is in the range of 0 to 200 ° C. Liquid crystallinity is generally confirmed by measurement with a differential scanning calorimeter. In the case of liquid crystal, the amount of heat accompanying the transition from solid to liquid crystal is observed at a certain temperature, and that temperature is called the solid-liquid crystal transition temperature. When the composite molecular alignment film of the present invention is used as an anion-sensitive film, it is desirable to use it at a temperature below the solid-liquid crystal transition temperature, more preferably at a temperature lower than the solid-liquid crystal transition temperature by 10 ° C. or more. When used above the solid-liquid crystal transition temperature, selectivity for various anions, particularly divalent anions, may be reduced. Compounds having a hydrophobic portion and a hydrophilic portion in one unit, such as the linear polymer of the present invention, are known to be oriented in a substantially constant direction when formed into a film. This fact can be confirmed by taking an X-ray diffraction photograph of the film.

In order to impart sensitivity to anions to the composite molecular alignment film of the present invention, it is desirable to immerse the alignment film in water containing metal ions at a temperature higher than its solid-liquid crystal transition temperature for 1 minute or more. By such an operation, metal ions can be immobilized in the composite molecular alignment film of the present invention, and properties as an anion-sensitive film can be exhibited. In addition, such an operation may increase the molecular orientation of the polymer and improve the response speed.

As the ion-selective electrode to which the ion-sensitive membrane of the present invention can be applied, one having a known structure is employed without any particular limitation. In general, a structure in which an internal standard electrode and an internal electrolytic solution are incorporated in a container in which at least a part of a part immersed in a sample solution is formed of the anion-sensitive membrane is preferable. A typical example is the structure shown in FIG.

In the electrode, materials other than the anion-sensitive film are not particularly limited, and conventional materials can be employed without any limitation. For example, as the material of the electrode cylinder, polyvinyl chloride, polymethyl methacrylate, etc., as the internal electrolyte, sodium chloride aqueous solution, potassium chloride aqueous solution, etc., as the internal reference electrode, platinum, gold, conductive material such as carbon graphite or the like. Insoluble metal chlorides such as silver-silver chloride and mercury-mercury chloride are used.

The ion-selective electrode to which the anion-sensitive membrane of the present invention can be applied is not limited to the structure shown in FIG. 1, but may have any structure as long as it has the anion-sensitive membrane. Examples of suitable other ion-selective electrodes include gold, platinum, a conductor such as graphite, or
An ion-selective electrode or the like constituted by attaching the anion-sensitive film to an ion conductor such as silver chloride or mercury chloride.

The ion-selective electrode using the anion-sensitive membrane of the present invention can be used by a known method. For example, the usage mode as shown in FIG. 2 is fundamental. That is, the ion-selective electrode 21 is immersed in the sample solution 23 together with the salt bridge 22, and the other end of the salt bridge is immersed in the saturated potassium chloride solution 26 together with the reference electrode 24. As the above-mentioned comparative electrode, a generally known electrode is employed. Examples of the electrode preferably used include a calomel electrode, a silver-silver chloride electrode, a platinum plate, and carbon graphite.

[0092]

The anion-sensitive film comprising the composite molecular orientation film of the present invention contains a hydrophobic calixarene compound capturing a cation as an ion-sensitive portion. Therefore,
The ion-sensitive part has a long life with little elution into water. Further, the selectivity of chloride ions with respect to fat-soluble anions such as nitrate ions, perchlorate ions, and thiocyanate ions is good, and it is possible to accurately determine chloride ions in biological fluids. From the above points, the industrial value of the composite molecular alignment film of the present invention is extremely large.

Examples will be given below to describe the present invention more specifically, but the present invention is not limited to these examples.

In the examples of the present invention, the weight fraction of the unit represented by the general formula [1] in the linear polymer is abbreviated as unit fraction.

Production Example 1 5 mmol of the monomers shown in Table 1 and 5 mg of azobisisobutyronitrile were placed in a test tube together with 10 ml of benzene and 10 ml of ethanol. After the test tube was placed in a nitrogen atmosphere, the tube was sealed and polymerized at 80 ° C. for 24 hours. The contents are methanol 50
The resulting precipitate was poured into 0 ml and collected by filtration. Drying under reduced pressure gave a solid as a polymer in the amount shown in Table 1. The unit fraction of the polymer was determined by elemental analysis. The results are summarized in Table 1.

[0096]

[Table 1]

[0097]

[Table 2]

[0098]

[Table 3]

[0099]

[Table 4]

[0100]

[Table 5]

[0101]

[Table 6]

Production Example 2 The following monomer (10 mmol) was used.

[0103]

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10 mmol of the monomer shown in Table 2 and 2 mg of azobisisobutyronitrile were put into a test tube together with 10 ml of a benzene-ethanol mixed solvent (1: 1, weight ratio).
After placing the test tube in a nitrogen atmosphere, stopper tightly and heat at 65 ° C for 3 hours.
Polymerization was carried out for 0 hour. The contents were poured into 500 ml of methanol and the resulting precipitate was collected by filtration. Drying under reduced pressure gave solids as polymers in the amounts shown in Table 3. The unit fraction of the polymer was determined by elemental analysis. Table 2 summarizes the results.

[0105]

[Table 7]

Production Example 3 An amount of 3 g of the monomer shown in Table 3 and hydroxyethyl methacrylate (hereinafter abbreviated as HEMA) shown in Table 3 and 3 mg of azobisisobutyronitrile were mixed in a benzene-ethanol mixed solvent (1: 1, weight by weight). Ratio) into a test tube with 10 ml. After the test tube was placed in a nitrogen atmosphere, the tube was sealed and sealed.
Polymerized at 30 ° C. for 30 hours. 500 ml of methanol
The precipitate formed was collected by filtration. By drying under reduced pressure, solids as polymers were obtained in the amounts shown in Table 3. The unit fraction of the hydrophobic polymer was determined by elemental analysis. Table 3 summarizes the results.

[0107]

[Table 8]

[0108]

[Table 9]

Production Example 4 Synthesis of 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrakis (octadecyloxycarbonyl) -methoxy-calix [4] arene (Compound No. 1) a) Synthesis of 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix [4] arene According to the method described in Journal of Organic Chemistry, vol.51,742 (1986). Therefore, 50 g of pt-butylphenol
(0.333 mol), 60 g (0.74 mol) of 37% formalin, 2 g of water
19.7 g (0.30 mol, 23%) of colorless square flakes were obtained from 0.64 g of sodium hydroxide (0.016 mol) dissolved in water.

B) 5,11,17,23-Tetra-t-butyl-25,26,2
Synthesis of 7,28-tetrakis (ethoxycarbonyl) -methoxy-calix [4] allene Journal of Chemical Society Chemical Communication
(1985) 388, 8.0 g (12.4 mmol) of compound a) and 11.4 g (11.4 g) of ethyl bromoacetate.
36 mmol) and 12.4 g (90 mmol) of anhydrous potassium carbonate,
6.3 g of colorless columnar crystals were obtained.

C) 5,11,17,23-Tetra-t-butyl-25,26,2
Synthesis of 7,28-tetrakis (octadecyloxycarbonyl) -methoxy-calix [4] arene 1 g (0.57 mmol) of the compound of the above b), 0.61 g (2.3 mmol) of stearyl alcohol, 0.1 g of p-toluenesulfonic acid
Was dissolved in 50 ml of benzene in a 100 ml eggplant flask. After refluxing at 80 ° C. for 2 hours with a Dean-Stark trap attached, the temperature was raised to 90 ° C. to evaporate benzene. When recrystallization was performed with toluene, unreacted stearyl alcohol was precipitated. This was removed by filtration. The filtrate was purified by column chromatography using a benzene / ethyl acetate mixed solvent to obtain 1.1 g of a white powder having the structure shown below.

[0112]

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Production Example 5 Synthesis of 5,11,17,23-tetramethoxymethyl-25,26,27,28-tetrakis (octadecyloxycarbonyl) -methoxy-calix [4] arene (Compound No. 2) a) 12. Synthesis of 25,26,27,28-tetrahydroxycalix [4] allene Compound of Preparation 4a) according to the method described in Journal of Organic Chemistry, vol. 50, 5802 (1985).
From 8 g (21.3 mmol) and 11 g (117 mmol) of phenol, 7.0 g (16.5 mmol) of white powder having the following structure was obtained.

[0114]

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B) Synthesis of 5,11,17,23-tetrakis [(dimethylamino) methyl]]-25,26,27,28-tetrahydroxycalix [4] arene Journal of American Chemical Society, vol. 110, 6153
(1988), 3.7 g (8.9 mmol) of compound a), dimethylamine (50% aqueous solution)
4.6 g (7.1 mmol) of a water-soluble white solid having the structure shown below was obtained from 3.9 g (45 mmol) and 3.5 g (45 mmol) of formalin.

[0116]

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C) 5,11,17,23-Tetramethoxymethyl-2
Synthesis of 5,26,27,28-tetrahydroxycalix [4] arene Journal of American Chemical Society, vol. 110,6153
According to the method described in (1988), 0.8 g (1.23 mmol) of the compound synthesized in b) above, 0.48 m of methyl iodide
1 (7.2 mmol) and 0.8 g of sodium methoxide gave 0.21 g (0.35 mmol) of a white solid having the structure shown below.

[0118]

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D) 5,11,17,23-tetramethoxymethyl-2
Synthesis of 5,26,27,28-tetrakis (ethoxycarbonyl) -methoxy-calix [4] arene 0.5 g (0.83 mmol) of the compound synthesized in c) above, 1.5 g (4.1 mmol) of ethyl bromoacetate, carbonic acid 0.6 g of potassium (4.
2 mmol) was placed in a 50 ml eggplant flask, 25 ml of acetone was added, and the mixture was heated and refluxed at 60 ° C. for 7 days in an oil bath. After the reaction, the solution was poured into ice water of 100 ml of 1N hydrochloric acid, and white precipitate was collected by decantation. The solid is dissolved in chloroform,
The mixture was filtered to remove insolubles. Purification was performed by column chromatography using ethyl acetate as a developing solvent to obtain 200 mg (0.21 mmol) of a viscous liquid having the following structure.

[0120]

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E) 5,11,17,23-tetramethoxymethyl-2
Synthesis of 5,26,27,28-tetrakis (octadecyloxycarbonyl) -methoxy-calix [4] arene 200 mg of the compound synthesized in the above d), 280 mg (1.1 mmol) of octadecyl alcohol, and 0.1 g of p-toluenesulfonic acid.
05 g was dissolved in 20 ml of toluene in a 50 ml eggplant flask. 80 minutes at 80 ° C in an oil bath and 6 minutes at 120 ° C
The mixture was heated under reflux for 0 minutes. Column chromatography was performed using a mixed solvent of chloroform / ethyl acetate as a developing solvent to obtain 350 mg (0.19 mmol) of a yellowish white powder having the following structure.

[0122]

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Production Example 6 Synthesis of 25,26,27,28-tetrakis (stearyloxycarbonyl) -methoxy-calix [6] arene-5,11,17,23-sulfonic acid (Compound No. 3) a) 25 Synthesis of potassium salt of 2,5,11,17,23-tetrasulfonic acid 37,38,39,40,41,42-Hexahydroxycalix [6]
Allen (purchased from Tokyo Chemical Industry Co., Ltd.) 2g (3.1mm
ol), 20% of 98% sulfuric acid, and 2.5 g (1.9 mmol) of 25,26,27,28-tetrahydroxycalix [6] arene-5,11,17,23 by the method described in JP-A-61-83156. -Potassium tetrasulfonate was obtained.

B) 25,26,27,28-Tetrakis (ethoxycarbonyl) -methoxy-calix [6] arene-5,11,1
Synthesis of 7,23-sulfonic acid 1 g of the compound of the above a)
(0.74 mmol), 2.5 g (15 mmol) of ethyl bromoacetate,
0.36 g (0.22 mm) of colorless crystals from 2 g of anhydrous potassium carbonate
ol) obtained.

C) 25,26,27,28-tetrakis (stearyloxycarbonyl) -methoxy-calix [6] arene
Synthesis of -5,11,17,23-sulfonic acid In the same manner as in Production Example 4c), the compound 0.
3 g (0.18 mmol), 0.45 g of stearyl alcohol (1.
6 mmol), 0.1 g to 0.21 g of p-toluenesulfonic acid
(0.07 mmol) of pale yellow powder of 25,26,27,28-tetrakis (stearyloxycarbonyl) -methoxy-calix [6] arene-5,11,17,23-sulfonic acid having the following structure: Was.

[0126]

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Production Example 7 Synthesis of 5,11,17,23-nitro-25,26,27,28-tetrakis (stearyloxycarbonyl) -methoxy-calix [4] arene (Compound No. 4) Production Example 4a) 2g (4.7mm) synthesized by the method of
ol) and 0.80 g (1.3 mmol) of 5,11,17,23-nitro-25,26,27,28-tetrahydroxycalix [4] arene by the method described in JP-A-61-291546.
Obtained. Thereafter, 5,11,17,23-nitro-25,26,27,28-tetrakis (stearyloxycarbonyl) -methoxy-calix [4] arene having the structure shown below was prepared according to the methods of Production Examples 6b) and c). 0.8 g (0.43 mmol) were obtained.

[0128]

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Production Example 8 Compound NO. 5 to NO. Synthesis of 9 5,11,17,23-tetra-t-butyl synthesized in Production Example 4b)
-25,26,27,28-tetrakis (ethoxycarbonyl) -methoxy-calix [4] allene (1 mmol), 6 mmol of the starting compound shown in Table 4, 0.1 g of p-toluenesulfonic acid
Was dissolved in 50 ml of benzene and the reaction was carried out according to the method of Preparation Example 4c) to give the corresponding 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrakis (alkoxycarbonyl) -methoxy- A calix [4] allene compound was obtained. Table 4 shows the yield and yield.
Are also shown.

[0130]

[Table 10]

Production Example 9 (Compound No. 10) A compound having the following structure was synthesized by the following methods a) to d).

[0132]

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A) Synthesis of 25,26,27,28-tetraacetoxycalix [4] arene 2 g of 25,26,27,28-tetrahydroxycalix [4] arene synthesized by the method of Production Example 4a) (4.7 mmol) was dispersed in 5 ml of acetic anhydride, and 0.1 g of 98% sulfuric acid was added dropwise, followed by stirring at 20 ° C. for 4 hours. 50 ml of water was added and the resulting precipitate was collected by filtration and 1.8 g (3.0 mmol) of 25,26,27,28-tetraacetoxycalix [4] arene as a white solid.
I got

B) 5,11,17,23-Tetraacetyl-25,26,2
Synthesis of 7,28-tetraacetoxycalix [4] arene 1.8 g of the compound of the above a) was dissolved in 60 ml of dichloromethane, 3.9 g of aluminum chloride and 4.2 ml of acetyl chloride were added, and the mixture was stirred at 0 ° C. for 3 hours. . This reaction solution was added to 20
Poured into 0 ml 0.5N hydrochloric acid and stirred vigorously. The dichloromethane layer was separated and evaporated under reduced pressure. The obtained solid was recrystallized from a mixed solvent of acetone and n-hexane to give a white solid 0.75.
g (0.99 mmol) was obtained.

C) 5,11,17,23-Tetracarboxy-25,26,
Synthesis of 27,28-tetraacetoxycalix [4] arene 0.7 g (0.92 mmol) of the compound b) was dissolved in 40 ml of dimethylformamide, and 1 ml of bromine and 2.3 g were dissolved.
A solution of sodium hydroxide in 10 ml of water was added dropwise with stirring. After stirring for 1 hour, the mixture was poured into 100 ml of 1N hydrochloric acid. The resulting solids were collected and washed with methanol.
2 g of 5,11,17,23-tetracarboxy-25,26,27,28-tetrahydroxycalix [4] arene (a pale yellow solid) was obtained. Further, the same operation as in a) was performed to obtain 0.2 g (0.26 mmol) of 5,11,17,23-tetracarboxy-25,26,27,28-tetraacetoxycalix [4] arene.

D) 0.2 g of compound c) and 0.39 g of lauryl bromide (1.5 g)
6 mmol) in acetone (30 ml) and sodium carbonate (3 g)
Was added and stirred at 60 ° C. for 72 hours. 1N reaction solution
The mixture was poured into 100 ml of hydrochloric acid, and the resulting solid was collected and purified by column chromatography to obtain compound 0.34 of the above structure.
g (0.18 mmol) was obtained.

Production Example 10 (Compound No. 11) Journal of American Chemical S
According to the method described in Japanese Society of Chemistry, vol. 110, No. 18, (1988) pages 6153 to 6162, starting from 5 g (12 mmol) of 25,26,27,28-tetrahydroxycalix [4] arene.
8 g (4.7 mmol) of 5,11,17,23-tetrakis (2-aminomethyl) -25.26.27,28-tetrahydroxycalix [4] arene was obtained. 50 ml of this compound in chloroform
, And 4.0 g of triethylamine was added. At room temperature, a solution of 2.4 g of acetyl bromide in 30 ml of chloroform was added dropwise. After stirring for 1 hour, the reaction solution was washed twice with 100 ml of water, and chloroform was distilled off. Recrystallization from a mixed solvent of acetone and hexane gave 1.8 g of a yellow solid. This compound was dissolved in 50 ml of chloroform, 2.0 g of triethylamine was added, and 30 ml of chloroform in which 4.5 g of stearoyl chloride had been dissolved was added dropwise. After stirring for 1 hour 10
After washing twice with 0 ml of water, chloroform was removed by distillation under reduced pressure. The resulting yellow solid was purified by column chromatography to give a pale yellow powder 0.3 of the structure shown below.
g (0.16 mmol) was obtained.

[0138]

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Production Example 11 Compound NO. 12 to NO. Synthesis of 21 According to the synthesis method shown in Production Examples 4 to 10, compounds having the structures shown in Table 5 were obtained. The starting material used was 25,26,27,28-tetrahydroxycalix [4] arene described in Preparation Example 5a). The main raw materials and yields are shown in Table 5.

[0140]

[Table 11]

[0141]

[Table 12]

[0142]

[Table 13]

[0143]

[Table 14]

Example 1 Polymer No. 1 produced in Production Examples 1 to 3 500 mg of the linear polymer of Nos. 1-32 and Calixarene No. produced in Production Example 4. 120 mg of the compound (1) was dissolved in 10 ml of chloroform and cast on a petri dish made of polytetrafluoroethylene (hereinafter abbreviated as PTFE). Chloroform 60
Evaporation was carried out under the conditions of ° C. and atmospheric pressure to obtain a uniform and transparent film. Each of the obtained anion-sensitive membranes was attached to an electrode as shown in FIG. 1, and then immersed in a 100 mM sodium chloride aqueous solution at 90 ° C. for 10 minutes. Using this, the relationship between the concentration at room temperature and the potential difference of various anions was measured by the apparatus shown in FIG. From the results obtained, a known method [G. J. See Moody, J .; D. Thomas, translated by Shin Munemori and Kazuo Nishiro, “Ion-selective electrode”, Kyoritsu Shuppan, 18
Page (1977)], the chloride ion selectivity coefficient for each anion was determined. The results are summarized in Table 6. As a comparative membrane, an ion-sensitive membrane containing polyvinyl chloride, methyl tridodecylammonium chloride and dibutyl phthalate [Analyitical Chemistry, 5
6,535-538 (1984)], and Table 6 also shows the chloride ion selectivity obtained in the same manner.

The smaller the value of the ion selectivity coefficient in this embodiment, the better the selectivity of the anion-sensitive membrane to chloride ions. As can be seen from Table 6, the ion-selective electrode using the anion-sensitive membrane of the present invention is:
It has excellent selectivity for chloride ions with respect to sulfate ions, phosphate ions, acetate ions, and hydrogen carbonate ions present in biological fluids, and is suitable for measuring chloride ion concentrations in biological fluids.

[0146]

[Table 15]

Example 2 The linear polymer No. 1 produced in Production Example 1 was used. Polymer 50 of 7
0 mg and the calixarene compound Nos. 2-No. 120 mg of the compound No. 21 was dissolved in 10 ml of chloroform and cast on a PTFE petri dish.
Chloroform was evaporated at 60 ° C. under atmospheric pressure to obtain a uniform and transparent film. Each of the obtained anion sensitive membranes was attached to an electrode as shown in FIG.
It was immersed in an aqueous solution of mM sodium chloride for 10 minutes. Using this, the relationship between the concentration at room temperature and the potential difference of various anions was measured by the apparatus shown in FIG. From the obtained results, the chloride ion selectivity was determined in the same manner as in Example 1. As a comparative example, measurement was performed using the same film as in Example 1. As can be seen from Table 7, which summarizes the results, the ion-selective electrode using the anion-sensitive membrane of the present invention is:
Excellent selectivity for chloride ion over phosphate ion, hydrogen carbonate ion, nitrate ion and thiocyanate ion.

[0148]

[Table 16]

Example 3 Film No. 1 was immersed in a 100 mM aqueous sodium chloride solution at 90 ° C. for 5 minutes, and then attached to the electrode as shown in FIG. Using this, the potential difference between the comparative electrode (calomel electrode) and the ion-selective electrode at 20 ° C. was measured using an aqueous solution of sodium chloride as a sample solution in the range of 10 ⁻⁴ to 10 ⁻¹ M using the apparatus shown in FIG. Table 8 and FIG. 3 show the relationship between the obtained potential difference and the chloride ion concentration of the sample solution. As can be seen from FIG. 3, the ion-selective electrode using the anion-sensitive membrane of the present invention shows a linear response in the range of 10 ^-4 to 10 ^-1 M. The potential gradient at this time was 58 mV / decade.
This value is calculated by Nernst equation: 59mV / decad
well matched with e. From this result, it is clear that the anion-sensitive membrane of the present invention has sufficient sensitivity to chloride ions.

[0150]

[Table 17]

Example 4 Film No. The anion-sensitive membrane No. 2 was immersed in a 100 mM aqueous sodium chloride solution at 90 ° C. for 5 minutes, and then attached to the electrode as shown in FIG. Using this, the potential difference between the comparative electrode (calomel electrode) and the ion-selective electrode at 20 ° C. was measured using an aqueous solution of sodium chloride as a sample solution in the range of 10 ⁻⁴ to 10 ⁻¹ M using the apparatus shown in FIG. The slope was calculated. . In addition, measurement was performed using a comparative film, and the results are also shown in Table 9. The same measurement was performed after storing this electrode in a 10 ^-1 M aqueous solution of sodium chloride for 30 days, and the results are shown in Table 9.

Table 9 shows that in the comparative film, the potential gradient was small and the sensitivity to chlorine ions was low. In contrast, the potential gradient of the anion-sensitive membrane of the present invention hardly changed even after 30 days, indicating that the electrode performance was maintained.

[0153]

[Table 18]

Application Examples The film Nos. Obtained in Examples 1 and 2 were used. 1, N
o. 33, no. 34 anion-sensitive membranes at 90 ° C.
After being immersed in a 0 mM sodium chloride aqueous solution for 10 minutes, it was attached to the electrode as shown in FIG. Using this, the output potential when 1 mM and 4 mM sodium chloride aqueous solutions were used as sample solutions was measured by the apparatus shown in FIG. From the measured values, a calibration curve of chloride ion concentration and output potential was prepared. On the other hand, sodium chloride 3 mM, sodium hydrogen carbonate 1 mM, sodium monohydrogen phosphate 1 mM, sodium nitrate 0.005 mM were used as test solutions.
The output potential was measured using an aqueous solution containing M and 10 mM sodium sulfate. The obtained value was substituted into the calibration curve to determine the chloride ion concentration. Table 10 shows the results. The chlorine ion concentration was similarly determined for the comparative film. Table 10 also shows the results.

[0155]

[Table 19]

As can be seen from Table 10, the measured values obtained using the anion-sensitive membrane of the present invention are in good agreement with the actual chloride ion concentration of 3 mM in the test solution. It is clear that the ion-selective electrode using the method can accurately measure the chloride ion concentration in a solution containing various anions.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing the configuration of an example of an ion-selective electrode using the anion-sensitive membrane of the present invention.

FIG. 2 is an explanatory diagram of an apparatus for measuring a potential difference using the ion-selective electrode of FIG.

FIG. 3 is a diagram showing a relationship between a chloride ion concentration measured in Example 3 and a potential difference.

[Explanation of symbols]

 Reference Signs List 11 electrode cylinder 12 ion-sensitive membrane 13 internal electrolyte 14 internal reference electrode 15 O-ring 21 ion-selective electrode 22 salt bridge 23 sample solution 24 reference electrode 25 electrometer 26 saturated potassium chloride aqueous solution 27 recorder

Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 33/24 C08L 33/24 C09K 3/00 C09K 3/00 C G01N 27/333 G01N 27/30 331A

Claims (1)

(57) [Claims] (A) General formula [1] In the formula, X is a nonionic monovalent group, having 1 carbon atom
One or two linear hydrophobic groups of 0 to 30, or directly connected
Carbon, carbon multiple bond, carbon-nitrogen multiple bond,
At least linked via a hydroxyl or amide bond
Carbon containing a divalent group composed of two aromatic rings in the chain
Having any one of the linear hydrophobic groups of Formulas 4 to 30
Of Y is Wherein R ³ is hydrogen or a methyl group;
² is a divalent group selected from -CO-, -COO-, -O- and -CONH-, n is an integer of 1 to 4, m represents an integer of 1 or 2, R ¹ is hydrogen, Methyl group, cyano group,
And a linear polymer containing 50% by weight or more of a unit represented by｝ representing a group selected from halogen atoms; and (B) a general formula [2] Ｉwhere i represents an integer of 4 to 8, and T represents Represents a group selected from and U is Or T represents a group selected from And U represents a group selected from the group consisting of A composite molecular alignment film comprising a calixarene compound represented by｝ representing a group selected from the group consisting of: