JPH04342733A - Conjugated molecule orientated film - Google Patents

Abstract

PURPOSE:To obtain a conjugated molecule orientated film suitable for anion- sensitive film providing an ion selective electrode measurable in high selectivity and stably, comprising a straight-chain polymer of a specific structure and a calyx arene compound having cation capturing ability. CONSTITUTION:A conjugated molecule orientated film comprising (A) a straight chain polymer containing >=50wt.% unit shown by formula I [X is nonionic monofunctional group containing one or two long-chain hydrophobic group or one straight chain hydrophobic group having a rigid part in the chain; Y is group shown by formula III, formula III, etc., (R<3> is H or methyl; R<2> is CO, COO, etc.; n is l-4; m is 1 or 2); R<1> is H, methyl, etc.] such as a homopolymer obtained by polymerizing a monomer shown by formula IV alone or a polymer obtained by copolymerizing two or more monomers and (B) a calyx arene compound shown by formula V (i is 4-8 integer; T is H, l-4C alkyl, NO2, etc.; U is X, group shown by formula VI, etc.) such as a material prepared by using a cyclic oligomer obtained by reacting a p-alkylphenol with formaldehyde under an alkali condition as a raw material.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a composite molecular alignment membrane that can be suitably used as an anion-sensitive membrane for use in an ion-selective electrode for analyzing ions in a solution.

0002

BACKGROUND OF THE INVENTION In medical care, it is common to measure sodium ions, potassium ions, and chloride ions in blood and urine and use these measurements for diagnosis. The concentration of specific ions in biological fluids is closely related to the metabolic mechanism of living organisms.
Various diagnoses such as hypertension symptoms, heart disease, neurological disorders, etc. can be made from the concentration of these ions. In recent years, it has become common to use ion-selective electrodes to measure these ions.

Generally, an ion-selective electrode consists of an electrode cylinder 1, which has an ion-sensitive membrane 12 as a boundary membrane in the part (generally the bottom) that is immersed in the sample liquid, as shown in FIG.
It is basically configured by providing an internal electrolytic solution 13 and an internal reference electrode 14 in the internal electrolyte 1.

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 and the salt bridge 22 are immersed in the sample solution 23, and the other end of the salt bridge is immersed together with the reference electrode 24 in the saturated potassium chloride solution 26. The potential difference between both electrodes is read by an electrometer 25, and the ionic activity of a specific ion species in the sample solution can be determined from the potential difference.

Conventionally, various membranes have been proposed as anion-sensitive membranes for selectively detecting anions, particularly chloride ions. If a solid membrane mainly composed of silver chloride contains bromide ions, cyanide ions, thiocyanate ions, etc. in the solution, the membrane surface will chemically change due to the influence of these ions, making it difficult to stabilize the potential, and in severe cases. may make it impossible to measure the potential. Furthermore, in measurements of various biological fluids, etc., they are easily affected by proteins, etc., and also have the drawback that the potential is not stable. Polymer membranes using quaternary ammonium salts as ion-sensitive substances have also been used, but they are heavily influenced by anions other than chlorine ions, such as phosphate ions and hydrogen carbonate ions, making accurate measurements difficult. It has the disadvantage that there are cases.

[0006] In addition, in recent years, anion-sensitive membranes have been proposed in which crown ether compounds are polymerized and cations are immobilized in the membrane (L. Angely, J. Simone).
t:New Journal of Chemistry
y, vol. 14, 83-86 H.S. (1990)
). Crown ether has a high ability to form complexes with cations,
Cations are immobilized in the membrane, and the membrane itself is considered to be an anion-sensitive membrane. Although this membrane shows a potential response to anions, it has drawbacks such as lack of mechanical strength and durability because it is a thin membrane, and a complicated membrane manufacturing method when making an anion-sensitive membrane. Was.

[0007]

SUMMARY OF THE INVENTION Accordingly, it has been desired to develop an anion-sensitive membrane that provides an ion-selective electrode capable of measuring chloride ions in biological fluids with high sensitivity and stability.

[0008]

[Means for Solving the Problems] The present inventors have conducted intensive research in order to develop an anion-sensitive membrane capable of solving the above problems. As a result, a composite molecular alignment film made of a polymer with a specific structure and a specific compound with cation-trapping ability has excellent ion sensitivity to chloride ions and good water resistance. The present inventors have discovered that an ion-selective electrode capable of measuring chloride ions with high sensitivity and stability can be obtained by using it as an anion-sensitive membrane, and have completed the present invention. Conventionally, anion-sensitive membranes in which an anion-sensitive substance made of a quaternary ammonium salt is dispersed in a carrier such as a polymer have been known, but anion-sensitive membranes in which a compound with cation-trapping ability is dispersed in a carrier are known. No sensitive membrane is known.

That is, the present invention provides a nonionic compound having either one or two long-chain hydrophobic groups, or one straight-chain hydrophobic group containing a rigid moiety in the chain. It is a monovalent group, and Y is

0010

[C7]

represents a group selected from (R3 is hydrogen or a methyl group, R2 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), R1 represents a group selected from hydrogen, methyl group, cyano group, and halogen atom}
A linear polymer containing 50% by weight or more of units represented by, and (B) general formula [2]

0012

[Chemical formula 8]

{Here, i represents an integer from 4 to 8, and T is

[0014]

[Chemical formula 9]

represents a group selected from and U is

0016
]

[Chemical formula 10]

or T represents a group selected from

[
0018

[Chemical formula 11]

represents a group selected from: and U is

00
20]

[Chemical formula 12]

The present invention provides a composite molecular alignment film containing a caraxarene compound represented by } representing a group selected from the following, and an anion-sensitive membrane comprising the alignment film. In the present invention, in the general formula [1],
It is a valent group (hereinafter abbreviated as a hydrophobic group). The presence of such hydrophobic groups in the polymer constituting the composite molecular alignment membrane of the present invention improves selective sensitivity when used as an anion-sensitive membrane, and improves stability when used in water. can be increased.

In the present invention, the long-chain hydrophobic groups among the hydrophobic groups are straight-chain alkyl groups having 10 to 30 carbon atoms or Preferably, it is a halogen-substituted product thereof. In addition, the long-chain hydrophobic group as used in the present invention includes not only completely linear groups but also branched groups having up to 2 carbon atoms. Preferred specific examples thereof include dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group.

[0023] One embodiment of the hydrophobic group of the present invention is one or two hydrophobic groups.
It has a long chain hydrophobic group. If there are three or more, it will be difficult to obtain raw materials or synthesize the polymer.

[0024] In another embodiment of the hydrophobic group of the present invention,
In a nonionic monovalent group having one linear hydrophobic group containing a rigid part in the chain, the rigid part is the following ■,
Examples include the groups shown in (1) and (2).

[0025] A divalent group consisting of at least two aromatic rings that are directly connected or connected via a carbon-carbon multiple bond, a carbon-nitrogen multiple bond, an ester bond, an amide bond, etc., and such a group. For example, if you show it concretely,

0
026]

[Chemical formula 13]

Examples include divalent groups such as ##STR1##.

■ A divalent group in which two aromatic rings have multiple bonds or a single bond between multiple atoms, and the rotation of which is energetically constrained; For example,

[0029]

[Chemical formula 14]

Examples include divalent groups such as ##STR1##.

[0031] ■ A divalent group in which aromatic rings form a condensation, and the rotation of the condensed rings is sterically constrained to each other when the condensed rings are stacked between multiple molecules, such a group To give a concrete example,

[0032]

[Chemical formula 15]

Examples include divalent groups such as ##STR1##.

[0034] The number of carbon atoms in the straight chain hydrophobic group of the hydrophobic group having one straight chain hydrophobic group containing a rigid part in the chain is determined by the water resistance and the ease of obtaining raw materials when used as an anion-sensitive membrane. It is preferable that it is 4-30. The number of carbon atoms referred to herein means the number of carbon atoms in the portion excluding the rigid portion and the bonding portion between the rigid portion and the linear hydrophobic group. The bond between the rigid portion and the linear hydrophobic group is generally preferably a carbon-carbon bond, an ester bond, or an ether bond. Limiting the number of straight-chain hydrophobic groups containing a rigid part in the chain to one is because if there are more than two, it will be extremely difficult to mix with the polymer and during the subsequent molding process, and it will also cause problems with the composite molecular alignment film. This is because it is undesirable because it often causes problems in stability.

The hydrophobic group of the present invention is not particularly limited as long as it satisfies the above requirements, and known ones can be used. Representative ones that are generally suitably used are specifically shown below.

0036]■

[0037]

[Chemical formula 16]

(However, R5 and R6 are the same or different straight chain alkyl groups having 12 to 30 carbon atoms or halogen-substituted products thereof, and D is -(E)f- and -(CH2)d-{
However, E is -Ph-, -Ph-O-, -Ph-OCO
represents a group selected from - and -Ph-COO- (where Ph represents a benzene ring and is bonded at the para position), f is 0 or 1, and d is a positive integer . }, a and b are positive integers. )■

[0039]

[Chemical formula 17]

(However, R5, R6, D, and a are the same as above, and k is 1 or 2.)■

[0041]

[Chemical formula 18]

(However, R5 and R6 are the same as above, and d is a positive integer.) ■ R7-V-G-
[6] (However, R7 is an alkyl group having 4 to 22 carbon atoms, an alkyloxy group, or an alkyloxycarbonyl group, or a halogen-substituted product thereof, and V is

[
0043

[Chemical formula 19]

{However, W is -N=CH-, -N=N-,
-CH=CH-, -NO=N-, -CONH-, -CO
O-, -O-, -CO-, -C(CH3)2-, Ph,
and -O-Ph-O- (Ph represents a benzene ring bonded at the para position), and j is 0 or 1. }, G represents a group selected from -(CH2)e
-, and -O-(CH2)e-. (However, e is a positive integer.)) The above general formula [3]
, [4], [5], and [6], d and e may be positive integers, but are generally preferably 1 to 16 from the viewpoint of easy availability of raw materials. Further, in the above general formula [3], a and b can be positive integers without any restriction, but are generally preferably 1 to 4 from the viewpoint of easy availability of raw materials. Furthermore, the above general formulas [3], [4], [5] and [6]
], examples of the halogen atom in the halogen-substituted alkyl group represented by R5 and R6 include fluorine, chlorine, bromine, and iodine atoms.

In the general formula [1], Y is

[0046]

[C20]

(R3 is hydrogen or methyl group, R2 is -C
It is a divalent group selected from O-, -COO-, -O-, and -CONH-, n is an integer of 1 to 4, and m is an integer of 1 or 2). The presence of these hydrophilic groups makes it possible to reduce the interference response of ions other than chloride ions when used as an anion-sensitive membrane. It is desirable that m is 1 or 2 from the viewpoints of ease of production, availability of raw materials, and durability in water when used as an anion-sensitive membrane.

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

(However, P is hydrogen, a halogen atom, a cyano group, an alkyl group, or a carboxyl group, and Q is an alkyl group, a carboxyl group, a phenyl group, a naphthyl group, an alkylcarboxyl group, an alkyloxycarbonyl group, an alkylamino group) carbonyl group, aminocarbonyl group, alkyloxy group, amino group, or alkylamino group.) The number of carbon atoms in the unit represented by the above general formula [7] depends on the ease of obtaining raw materials and the production of the resulting polymer. Considering the membrane property, 1
It is preferably 0 or less.

In the linear polymer constituting the composite molecular alignment film of the present invention, the weight fraction of the unit represented by the general formula [1] based on the total polymer is preferably 50% by weight or more. If the fraction of the above unit is less than 50% by weight, the ion selectivity when used as an anion-sensitive membrane may be insufficient, and the stability when used in water may deteriorate. Further, the molecular weight of the linear polymer is not particularly limited, but it is preferable that the number average molecular weight is 5,000 or more. If the number average molecular weight is 5000 or less, the membrane becomes brittle.

[0051] The method for producing the linear polymer is not particularly limited and any known method may be adopted, but generally, monomers having the structure represented by the following general formula [8] are homopolymerized or two types of monomers are polymerized. It can be obtained by copolymerizing the above.

[0052]

[C21]

The definitions and preferred examples of X, Y, and R1 are as described above. Although the monomer represented by the general formula [8] may be polymerized alone, it is also possible to copolymerize the monomer with a copolymerizable vinyl monomer to obtain a linear chain suitable for the composite molecular alignment film of the present invention. It is possible to obtain a polymer in the form of As the vinyl monomer copolymerizable with the monomer represented by general formula [8], known monomers can be used without particular limitation. Typical examples that are generally preferably used 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 Examples include vinyl ether compounds such as ether.

[0054] The polymerization method for producing the above-mentioned linear polymer may be ionic polymerization or radical polymerization, but it is preferable to carry out the polymerization in the presence of a radical initiator. As for the polymerization operation, generally known operations can be used without particular restriction, but
Solution polymerization is preferably used from the viewpoints of uniformity of the obtained polymer and ease of controlling the composition ratio of the copolymer. The solvent for solution polymerization is not particularly limited as long as it dissolves the monomers used. Those generally preferably used include water, methanol, ethanol, acetone, benzene, dimethylformamide, dichloromethane, tetrachloromethane, chloroform, tetrahydrofuran, dichloroethane, and chlorobenzene. Two or more of the above solvents may be used in combination. The polymerization temperature is preferably 0°C to 150°C, and preferably 40°C to
100°C is more preferred.

Various methods known in the art can be used to isolate the linear polymer, but in the case of solution polymerization, the reaction mixture is poured into a solvent that does not dissolve the produced polymer. A reprecipitation method is preferred.

The linear polymer produced as described above is generally a colorless, white or pale yellow solid. Although it is sparingly soluble in water, it dissolves in organic solvents such as dimethylformamide, chloroform, tetrachloromethane, dichloromethane, tetrachloroethane, and tetrahydrofuran at room temperature to 100°C. Incidentally, the content of the unit represented by the above-mentioned 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 are sometimes called calix[i]arenes (i is an integer from 4 to 8). It is known that the calixarene compound represented by the general formula [2] has a strong ability to capture specific cations. Since the cation is captured by the oxygen atom bonded to the benzene ring, the radius of the ion at which the capture ability is maximized 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 a calixarene compound in the composite molecular alignment film of the present invention exhibits anion sensitivity. The calixarene compound of general formula [2] is
Since either U or T contains a hydrophobic group represented by X, it has good affinity with the hydrophobic group in the polymer and is immobilized in the polymer. In addition, the presence of the hydrophobic group suppresses elution of the calixarene compound into water, and when used as an anion-sensitive membrane, the storage stability and potential stability in water become good.

Although the mechanism by which anion sensitivity is expressed due to the presence of a calixarene compound is not clear, the cations captured by the calixarene compound are immobilized in the membrane, resulting in anion exchange membrane This is thought to be because it functions as a.

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

When the composite molecular alignment membrane of the present invention is used as an anion-sensitive membrane, 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. It is preferable. . More preferably, the amount is in the range of 10 to 30 parts by weight per 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 will deteriorate, and if the amount is more than 40 parts by weight, the resulting membrane will become brittle.

As the calixarene compound used in the present invention, the compound represented by the general formula [2] can be used without any limitation, but preferred specific examples thereof include:
5,11,17,23-tetra-t-butyl-25,2
6,27,28-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, 2
5,26,27,28-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] allene, 5,11,17,23-tetra-methoxymethyl-25,26,27,28-tetrakis(ethoxycarbonyl)-methoxy-calix [8] Allen, 5,11,17,23-tetra-lauryloxymethyl-25,26,27,28-tetrakis(ethoxycarbonyl)-methoxy-calix [4]
Examples include Allen.

The method for producing calixarene represented by the general formula [2] is not particularly limited, and any known method may be employed. D. Edited by Gutsche “Calixaren”
es” (1989 The Royal Society
y of Chemistry), Tetrahedr
on vol. 42, p1636, JP-A-61-831
56, JP-A-61-291546, Journalof
Organic Chemistry, vol. 51
, p742 (1986), Journal of O
rganic chemistry, vol. 50,p
5802 (1985), Journal of Am
Erican Chemical Society,v
ol. 110, p6153 (1988), Journal
alof Chemical Society Che
mical Communication p388 (
This can be carried out by the method described in (1985) et al.

Generally, a cyclic oligomer (p-alkylhydroxycalixarene) obtained by reacting p-alkylphenol and formaldehyde under alkaline conditions is used as a starting material. As p-alkylphenol, p-t-butylphenol and p-t-octylphenol are generally used because of their high production yield and easy availability of raw materials. Furthermore, if the number of carbon atoms in the alkyl group is 10 or more, the yield of the cyclic oligomer will be significantly lowered due to steric hindrance, which is not preferable. The reaction temperature is preferably 150°C or higher and 300°C or lower. If the temperature is too low, linear oligomers will mainly be produced and cyclic oligomers will not be obtained, and if the temperature is too high, by-products other than oligomers will increase, resulting in a decrease in production yield, which may pose a danger to the synthesis reaction operation. This is because it also increases. As the solvent, diphenyl ether whose boiling point is higher than the reaction temperature is preferably used. This cyclic oligomer is a white powder with a high melting point and is a mixture of tetramers to octamers. From this mixture, each of the cyclic oligomers of tetramers to octamers can be obtained by recrystallization using a solvent such as benzene, toluene, or ethyl acetate, or by column chromatography. Its general formula is shown below.

[0065]

[C22]

(i is an integer of 4 to 8, and R8 represents an alkyl group.) Furthermore, the hydroxycalixarene represented by the following general formula [9] obtained by removing the alkyl group from this compound is useful for derivatization. It is a compound. This compound can be obtained by reacting the above p-alkyl calixarene with an equivalent or more amount of phenol in a solvent in the presence of a Lewis acid to carry out a transfer reaction of the alkyl group. Examples of suitable solvents include benzene, toluene, and nitrobenzene, and examples of Lewis acids include aluminum chloride and boron trifluoride. The reaction temperature is not particularly limited as long as it is around room temperature, but it is preferably carried out at 10°C or higher and 40°C or lower.

[0067]

[C23]

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

All of the following reactions are 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 ease of solvent removal after the reaction and 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. Moreover, these compounds can be separated and purified by column chromatography.

■T=-CH2R9 (R9 represents an alkyl group having 1 or more carbon atoms) Hydroxycalixarene of the general formula [9] is reacted with an acid chloride having an alkyl group of R9 to esterify the phenol group. Furthermore, a Fries rearrangement reaction is carried out by reacting this compound with a large excess of aluminum chloride. Then Wolf-K using hydrazine
It can be obtained by performing isher reduction.

■T=-CH2N(R4)2,-CH2N
XR4 (R4 is as defined in general formula [2] and It can be obtained by reaction with dialkylamine and formaldehyde.

■T=-CH2OR4, -CH2OX The calixarene compound obtained in step (1) above is reacted with alkyl iodide in a polar solvent such as dimethyl sulfoxide,
It can then be obtained by reacting with a compound represented by R4ONa or XONa.

■T=-COOR4, -COOX general formula [
9] is reacted with acetic anhydride in the presence of an acid catalyst to obtain an acetyl compound. Sulfuric acid and nitric acid are used as acid catalysts. Acylation is then carried out in a Friedel-Crafts reaction with acetyl bromide under a Lewis acid catalyst. The obtained compound was dissolved in dimethylformamide, an aqueous solution containing bromine and sodium hydroxide was added,
Neutralize with acid. After that, R4Z, or XZ (
(Z represents a halogen atom) to obtain the target compound.

■T=-CH2CH2NHCOR4 The above ■
The calixarene compound obtained 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. The target compound is obtained by reacting this with an alkyl acid chloride compound represented by R4COCl.

■T=-SO3H It can be obtained by heating the calixarene compound of the general formula [9] to 80° C. or higher in 90% sulfuric acid.

(2) T=-NO2 The sulfonated calixarene obtained in the above (1) is poured into nitric acid having a concentration of 30 to 70% and at a temperature of 10° C. or lower to carry out a reaction of substitution of sulfone groups with nitro groups.

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

[0078] After introducing the substituent T into the calixarene compound of the general formula [9] by the above-mentioned methods 1 to 2, the method for further introducing the substituent U in the general formula [2] into the calixarene compound is described below. state

All of the following reactions are carried out in a solvent. The solvent can be used without particular limitation as long as it does not participate in the reaction, but ease of solvent removal after the reaction,
Toluene, benzene, acetone, ethyl acetate, etc. are preferably used in consideration of the solubility of the raw materials. 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. Moreover, these compounds can be separated and purified by column chromatography.

■U=-X, -R4, -COX, -COR
4 in the presence of a base in a solvent, various tetrahydroxycalixarene compounds obtained by the above method and XZ, R4Z,
It can be obtained by reaction with a compound represented by ZCOX or ZCOR4 (Z represents a halogen atom such as a chlorine atom or a bromine atom). The base used is XZ
, in the reaction with R4Z, inorganic alkali salts, ZCOX, ZC
A tertiary amine compound is preferably used in the reaction with OR4. Specific examples include inorganic alkali salts such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, etc.
Examples of tertiary amine compounds include trimethylamine and triethylamine.

[0081] U=-CH2COOX, -CH2COOR4 ZCH2COOX, ZCH2COOR4 in the presence of a base in a solvent
It can be obtained by reacting with a compound represented by (Z is as above). Alternatively, a method may be used in which R4 and X are replaced by a transesterification reaction with a compound represented by XOH after reacting with ZCH2COOR4.

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. Although it is sparingly soluble in water, it is soluble in organic solvents such as dimethylformamide, chloroform, tetrachloromethane, dichloromethane, tetrachloroethane, and tetrahydrofuran.
Dissolves at room temperature to 100°C.

[0083] The method for forming the mixture of the linear polymer and calixarene compound obtained by the above production method into a membrane is not particularly limited, and any method may be used. Examples of generally preferred methods are as follows.

A film-like product is obtained by dissolving the linear polymer and calixarene compound of the present invention in a soluble solvent, casting the solution onto a suitable substrate, and then removing the solvent. The solvent used here is not particularly limited as long as it dissolves the linear polymer and calixarene compound of the present invention, but the soluble solvents described in the above polymer production method are preferably used. To remove the above-mentioned solvent, air drying, vacuum drying, etc. are generally used without particular limitation.

The thickness of the composite molecular alignment film of the present invention is not particularly limited, but is generally 0.1 μm to 5 mm, preferably 5 mm.
A range of from 100 μm is preferable since sufficient membrane strength can be imparted when used in an anion-sensitive membrane.

The anion-sensitive membrane of the present invention generally often exhibits liquid crystallinity as its basic property. The temperature range in which liquid crystallinity is exhibited is in the range of 0 to 200°C. Liquid crystallinity is generally confirmed by measurement using a differential scanning calorimeter. In the case of a 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 above-mentioned solid-liquid crystal transition temperature, more preferably at least 10° C. lower than the solid-liquid crystal transition temperature. When used at temperatures above the solid-liquid crystal transition temperature, the selectivity for various anions, particularly divalent anions, may be reduced. It is known that in compounds having a hydrophobic part and a hydrophilic part in one unit, such as the linear polymer of the present invention, each unit is 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-like material.

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 above its solid-liquid crystal transition temperature for one minute or more. Through such operations, metal ions can be immobilized in the composite molecule-oriented membrane of the present invention, allowing it to exhibit properties as an anion-sensitive membrane. Further, such an operation may increase the molecular orientation of the polymer, resulting in an improvement in response speed.

[0088] The ion-selective electrode to which the ion-sensitive membrane of the present invention can be applied may have any known structure without any particular limitations. Generally, it is preferable to have a structure in which an internal standard electrode and an internal electrolyte are housed in a container in which at least a portion of the part to be immersed in the sample solution is constituted by the anion-sensitive membrane. A typical example is the structure shown in FIG. 1 above.

[0089] The material of the electrode other than the anion-sensitive membrane is not particularly limited, and conventional materials may be used without limitation. For example, the electrode cylinder material may be polyvinyl chloride, polymethyl methacrylate, etc., the internal electrolyte may be a sodium chloride aqueous solution, potassium chloride aqueous solution, etc., and the internal reference electrode may be a conductive material such as platinum, gold, carbon graphite, etc. Slightly soluble 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 other suitable ion-selective electrodes include conductors such as gold, platinum, and graphite;
These are ion-selective electrodes, etc., which are constructed by pasting the anion-sensitive membrane on an ion conductor such as silver chloride or mercury chloride.

Further, the ion-selective electrode using the anion-sensitive membrane of the present invention can be used in a known manner. For example, the usage mode as shown in FIG. 2 described above is basic. That is, the ion-selective electrode 21 is immersed together with the salt bridge 22 in the sample solution 23, and the other end of the salt bridge is immersed together with the comparison electrode 24 in the saturated potassium chloride solution 26. As the above-mentioned reference electrode, generally known ones are employed, and examples of those preferably used include a calomel electrode,
These include silver-silver chloride electrodes, platinum plates, carbon graphite, etc.

[0092]

Effects of the Invention The anion-sensitive membrane comprising the composite molecular alignment membrane of the present invention contains a hydrophobic calixarene compound that captures cations as an ion-sensitive moiety. Therefore,
The ion-sensitive part hardly elutes into water and has a long life. Furthermore, the selectivity of chloride ions to fat-soluble anions such as nitrate ions, perchlorate ions, and thiocyanate ions is good, and it is possible to accurately quantify 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 are given below to explain 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 monomer 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 placing the inside of the test tube under a nitrogen atmosphere, the test tube was sealed tightly and polymerized at 80° C. for 24 hours. The contents were poured into 500 ml of methanol and the resulting precipitate was collected by filtration. By drying under reduced pressure, a solid polymer was obtained 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 10 mmol of the monomer shown below and

[0103]

[C24]

10 mmol of the monomer shown in Table 2 and 2 mg of azobisisobutyronitrile were placed in a test tube together with 10 ml of a benzene-ethanol mixed solvent (1:1, weight ratio). After putting the inside of the test tube under a nitrogen atmosphere, seal it tightly and incubate at 65℃ for 3 days.
Polymerization was carried out for 0 hours. The contents were poured into 500 ml of methanol and the resulting precipitate was collected by filtration. By drying under reduced pressure, a solid polymer was obtained in the amount shown in Table 3. The unit fraction of the polymer was determined by elemental analysis. The results are summarized in Table 2.

[0105]

[Table 7]

Production Example 3 3 g of the monomer shown in Table 3, hydroxyethyl methacrylate (hereinafter abbreviated as HEMA) in the amounts shown in Table 3, and 3 mg of azobisisobutyronitrile were mixed in a benzene-ethanol mixed solvent (1:1, by weight). ratio) and 10 ml into a test tube. After placing the inside of the test tube under a nitrogen atmosphere, the test tube was sealed tightly and polymerized at 60° C. for 30 hours. Dilute the contents with methanol 50%
The precipitate formed was collected by filtration. By drying under reduced pressure, solid matter as a polymer was obtained in the amount shown in Table 3. The unit fraction of the hydrophobic polymer was determined by elemental analysis. The results are summarized in Table 3.

[0107]

[Table 8]

[0108]

[Table 9]

Production Example 4 5,11,17,23-tetra-t-butyl-25,2
Synthesis of 6,27,28-tetrakis(octadecyloxycarbonyl)-methoxy-calix[4]arene (compound No. 1) a) 5,11,17,23-tetra-t-butyl-25,26,27, Synthesis of 28-tetrahydroxycalix[4]arene Journal
of Organic Chemistry, vol.
51,742 (1986), 50 g (0.333 mol) of pt-butylphenol was added.
), 37% formalin 60g (0.74mol), water 2
0.64 g of sodium hydroxide (0.01
6 mol) to 19.7 g (0.30 mol, 23%)
Colorless square flakes were obtained.

b) 5,11,17,23-tetra-t-
Synthesis of butyl-25,26,27,28-tetrakis(ethoxycarbonyl)-methoxy-calix[4]arene Journal of Chemical Society
ty Chemical Communication
(1985) 388, 6.3 g of the above compound a) from 8.0 g (12.4 mmol), 11.4 g (136 mmol) of ethyl bromoacetate, and 12.4 g (90 mmol) of anhydrous potassium carbonate. Colorless columnar crystals were obtained.

c) 5,11,17,23-tetra-t-
Butyl-25,26,27,28-tetrakis(octadecyloxycarbonyl)-methoxy-calix [4
] Synthesis of allene 1 g (0.57 mmo) of the compound b) above
l), stearyl alcohol 0.61g (2.3mmol
l), 0.1 g of p-toluenesulfonic acid was dissolved in 50 ml of benzene in a 100 ml eggplant flask. Dean
- A Stark trap was attached and reflux was performed at 80°C for 2 hours, and then the temperature was raised to 90°C to evaporate benzene. When recrystallized with toluene, unreacted stearyl alcohol precipitated and was removed by filtration. The filtrate was purified by column chromatography using a benzene/ethyl acetate mixed solvent to obtain a white powder with the structure shown below.
I got 1g

[0112]

[C25]

Production Example 5 5,11,17,23-tetramethoxymethyl-25,
Synthesis of 26,27,28-tetrakis(octadecyloxycarbonyl)-methoxy-calix[4]arene (Compound No. 2) a) Synthesis of 25,26,27,28-tetrahydroxycalix[4]arene Journal of Organic Chemis
try, vol. 50, 5802 (1985), 13.8 g of the compound of Preparation Example 4a)
(21.3 mmol) and phenol 11 g (117 mmol)
ol), 7.0 g of white powder with the structure shown below (16.
5 mmol) was obtained.

[0114]

[C26]

b) 5,11,17,23-tetrakis [
(dimethylamino)methyl)]-25,26,27,2
Synthesis of 8-tetrahydroxycalix[4]arene Journal of American Chemi
cal Society, vol. 110,6153(
1988), 3.7 g (8.9 mmol) of the compound a) above and dimethylamine (5
0% aqueous solution) 3.9 g (45 mmol), formalin 3
．． 4.6 g (7.1 mmol) of a water-soluble white solid having the structure shown below was obtained from 5 g (45 mmol).

[0116]

[C27]

c) Synthesis of 5,11,17,23-tetramethoxymethyl-25,26,27,28-tetrahydroxycalix[4]arene Journal of American Chemi
cal Society, vol. 110,6153(
b) above according to the method described in 1988).
From 0.8 g (1.23 mmol) of the compound synthesized in step 1, 0.48 ml (7.2 mmol) of methyl iodide, and 0.8 g of sodium methoxide, a white solid with the structure shown below was obtained.
21 g (0.35 mmol) was obtained.

[0118]

[C28]

d) Synthesis of 5,11,17,23-tetramethoxymethyl-25,26,27,28-tetrakis(ethoxycarbonyl)-methoxy-calix[4]arene 0.5 g of the compound synthesized in c) above (0.83 mmol
), 1.5 g (4.1 mmol) of ethyl bromoacetate, and 0.6 g (4.2 mmol) of potassium carbonate were placed in a 50 ml eggplant flask, and 25 ml of acetone was added thereto.
The mixture was heated under reflux at ℃ for 7 days. After the reaction, add 1 part of 1N hydrochloric acid to the solution.
The white precipitate was collected by decantation. The solid was dissolved in chloroform and filtered to remove insoluble matter. Purified by column chromatography using ethyl acetate as a developing solvent, a viscous liquid 2 with the structure shown below was obtained.
00 mg (0.21 mmol) was obtained.

[0120]

[C29]

e) 5,11,17,23-tetramethoxymethyl-25,26,27,28-tetrakis(octadecyloxycarbonyl)-methoxy-calix [
4] Synthesis of allene 200 mg of the compound synthesized in d) above
, 280 mg (1.1 mmol) of octadecyl alcohol
), 0.05 g of p-toluenesulfonic acid was dissolved in 20 ml of toluene in a 50 ml eggplant flask. 8 in oil bath
Heating and refluxing was performed at 0°C for 80 minutes and then at 120°C for 60 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 structure shown below.

[0122]

[C30]

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

b) 25,26,27,28-tetrakis(ethoxycarbonyl)-methoxy-calix [6]
Synthesis of allene-5,11,17,23-sulfonic acid 1 g of the above compound a) was prepared in the same manner as in Production Example 4b).
(0.74 mmol), ethyl bromoacetate 2.5 g (1
5 mmol), 0 colorless crystals from 2 g of anhydrous potassium carbonate
．． 36 g (0.22 mmol) was obtained.

c) Synthesis of 25,26,27,28-tetrakis(stearyloxycarbonyl)-methoxy-calix[6]arene-5,11,17,23-sulfonic acid The above procedure was carried out in the same manner as in Production Example 4c). 0.3 g (0.18 mmol) of the compound b), 0.45 g (1.6 mmol) of stearyl alcohol, and 0.1 g to 0.21 g (0.07 mmol) of p-toluenesulfonic acid 25,26 with the structure shown below. ,27,28-tetrakis(stearyloxycarbonyl)-methoxy-calix [
6] A pale yellow powder of arene-5,11,17,23-sulfonic acid was obtained.

[0126]

[Chemical formula 31]

Production Example 7 5,11,17,23-nitro-25,26,27,2
Synthesis of 8-tetrakis(stearyloxycarbonyl)-methoxy-calix[4]arene (compound No. 4) 2 g of the compound synthesized by the method of Production Example 4a) (4.
7 mmol) to published patent publication JP-A-61-29154
5,11,17,23-nitro-2 by the method described in 6.
5,26,27,28-tetrahydroxycalix [
4] 0.80 g (1.3 mmol) of arene was obtained. Thereafter, according to the method of Production Example 6b) and c), 5 of the structure shown below.
,11,17,23-nitro-25,26,27,28
-Tetrakis(stearyloxycarbonyl)-methoxy-calix[4]arene, 0.8g (0.43mm
ol) Obtained.

[0128]

[C32]

Production Example 8 Compound No. 5~NO. 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrakis(ethoxycarbonyl)-methoxy-calix [4] synthesized in Production Example 4b) of 9
1 mmol of allene and 6 m of the raw material compounds shown in Table 4
mol, 0.1 g of p-toluenesulfonic acid was dissolved in 50 ml of benzene and reacted according to the method of Production Example 4c) to obtain the corresponding 5,11,17,23-tetra-t-butyl-25,26,27, A 28-tetrakis(alkoxycarbonyl)-methoxy-calix[4]arene compound was obtained. The yield and yield are also shown in Table 4.

[0130]

[Table 10]

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

[0132]

[Chemical formula 33]

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

b) Synthesis of 5,11,17,23-tetraacetyl-25,26,27,28-tetraacetoxycalix[4]arene Dissolve 1.8 g of the compound in a) above in 60 ml of dichloromethane, 3. 9 g of aluminum chloride and 4.2 ml of acetyl chloride were added and stirred at 0° C. for 3 hours. This reaction solution was poured into 200 ml of 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 0.75 g (0.99 mmol) of a white solid.
) was obtained.

c) Synthesis of 5,11,17,23-tetracarboxy-25,26,27,28-tetraacetoxycalix[4]arene 0.7 g of the compound b) above (
0.92 mmol) was dissolved in 40 ml of dimethylformamide, and a solution of 1 ml of bromine and 2.3 g 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 solid was collected and washed with methanol, and 0.2 g of 5,
11,17,23-tetracarboxy-25,26,2
7,28-tetrahydroxycalix[4]arene (
A pale yellow solid) was obtained. Furthermore, perform the same operation as in a).
,11,17,23-tetracarboxy-25,26,
0.2 g (0.26 mmol) of 27,28-tetraacetoxycalix[4]arene was obtained.

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

Production Example 10 (Compound No. 11) Journal of Amer
ican Chemical Society vol.
．． 110, No. 18, (1988) 6153-616
According to the method described on page 2, 2.8 g (4.7 mmol) of 25,26,27,28-tetrahydroxycalix[4]arene was used as a starting material.
1) 5,11,17,23-tetrakis(2-aminomethyl)-25.26.27,28-tetrahydroxycalix[4]arene was obtained. This compound was dissolved in 50 ml of chloroform, and 4.0 g of triethylamine was added. A solution of 2.4 g of acetyl bromide in 30 ml of chloroform was added dropwise at room temperature. After stirring for 1 hour, the reaction solution was
After washing twice with 0 ml of water, chloroform was distilled off. Recrystallize with acetone/hexane mixed solvent to obtain a yellow solid 1.
8g was obtained. 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, the mixture was washed twice with 100 ml of water, and chloroform was removed by distillation under reduced pressure. The obtained yellow solid was purified by column chromatography to obtain 0.3 g (0.16 mmol) of pale yellow powder having the structure shown below.

[0138]

[C34]

Production Example 11 Compound No. 12~NO. Compounds having the structures shown in Table 5 were obtained according to the synthesis methods shown in Synthesis Examples 4 to 10 of No. 21. 25,26,27,28-tetrahydroxycalix[4]arene as described in Preparation Example 5a) was used as starting material. The main raw materials and yields are also 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 linear polymers Nos. 1 to 32 and Calixarene No. 1 prepared in Production Example 4. 120 mg of compound 1 was dissolved in chloroform 10
ml of polytetrafluoroethylene (hereinafter referred to as PTF).
It is abbreviated as E. ) was cast onto a petri dish. Chloroform was evaporated at 60° 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, Figure 2
The relationship between the concentration and potential difference at room temperature was measured for various anions using the apparatus shown in . From the obtained results, a known method [G. J. Moody, J. D. Thomas
The chloride ion selectivity coefficient for each anion was determined by the method described in "Ion Selective Electrode" by Author, Makoto Munemori, translated by Kazuo Nikiro, Kyoritsu Shuppan, p. 18 (1977)]. The results are summarized in Table 6. As a comparative membrane, an ion-sensitive membrane [Analyiti
cal Chemistry, 56, 535-538 (
Table 6 also shows the chloride ion selectivity coefficients determined in a similar manner for the chlorine ions described in 1984).

The ion selection coefficient in this example indicates that the smaller the value, 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 chlorine ions over sulfate ions, phosphate ions, acetate ions, and bicarbonate ions present in biological fluids, and is suitable for measuring chloride ion concentrations in biological fluids.

[0146]

[Table 15]

Example 2 Linear polymer No. 2 produced in Production Example 1 7 polymer 50
0 mg and calixarene compound No. 0 mg produced in Production Examples 5 to 11. 2~No. 120 mg of compound No. 21 was dissolved in 10 ml of chloroform and cast in a PTFE petri dish. Chloroform was evaporated at 60° C. and atmospheric pressure to obtain a uniform and transparent film. After each of the obtained anion-sensitive membranes was attached to an electrode as shown in FIG.
It was immersed in an mM sodium chloride aqueous solution for 10 minutes. Using this, the relationship between the concentration and potential difference at room temperature was measured for various anions using the apparatus shown in FIG. From the results obtained, the selectivity coefficient for chloride ions was determined in the same manner as in Example 1. As a comparative example, the same membrane as in Example 1 was used for measurement. As can be seen from Table 7, which summarizes the results, the ion-selective electrode using the anion-sensitive membrane of the present invention has
Excellent selectivity for chlorine ions over phosphate ions, bicarbonate ions, nitrate ions, and thiocyanate ions.

[0148]

[Table 16]

Example 3 Membrane No. The anion-sensitive membrane No. 1 was immersed in a 100 mM sodium chloride aqueous solution at 90° C. for 5 minutes, and then attached to an electrode as shown in FIG. Using this and the apparatus shown in Figure 2, 10-
The potential difference between a reference electrode (calomel electrode) and an ion-selective electrode was measured at 20° C. using an aqueous sodium chloride solution in the range of 4 to 10 −1 M as a sample solution. 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 exhibits a linear response in the range of 10-4 to 10-1M. Also, the potential gradient at this time is 58mV/dec
It was ade. This value is a calculated value of 59 mV/d determined by the Nernst equation.
It is in good agreement with ecade. 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 Membrane No. The anion-sensitive membrane of No. 2 was immersed in a 100 mM sodium chloride aqueous solution at 90° C. for 5 minutes, and then attached to an electrode as shown in FIG. Using this and the apparatus shown in Figure 2, 10-
The potential difference between a reference electrode (calomel electrode) and an ion-selective electrode was measured at 20° C. using an aqueous sodium chloride solution in the range of 4 to 10 −1 M as a sample solution, and the potential gradient was calculated. . Measurements were also carried out using comparative membranes, and the results are also shown in Table 9. Further, after storing this electrode in a 10-1M sodium chloride aqueous solution for 30 days, similar measurements were performed, and the results are shown in Table 9.

Table 9 shows that in the comparative membrane, the potential gradient is smaller and the sensitivity to chlorine ions is lower. 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 Example Membrane No. 1 obtained in Examples 1 and 2 described above. 1, N
o. 33, No. 34 anion-sensitive membranes at 90°C.
Figure 1 after immersion in 0mM sodium chloride aqueous solution for 10 minutes.
It was attached to the electrode as shown in the figure. Using this and the apparatus shown in FIG. 2, the output potential was measured when 1 mM and 4 mM sodium chloride aqueous solutions were used as sample solutions. A calibration curve of chloride ion concentration and output potential was created from the measured values. On the other hand, as a test solution, sodium chloride 3mM, sodium hydrogen carbonate 1
The output potential was measured using an aqueous solution containing 1 mM of sodium monohydrogen phosphate, 0.005 mM of sodium nitrate, and 10 mM of sodium sulfate. The obtained values were substituted into the calibration curve to determine the chloride ion concentration. The results are shown in Table 10. The chloride ion concentration was determined in the same manner for the comparative membrane. The results are also shown in Table 10.

[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 this method can accurately measure the chloride ion concentration in solutions containing various anions.

[Brief explanation of 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. 1;

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

[Explanation of symbols]

11 Electrode cylinder 12 Ion sensitive membrane 13 Internal electrolyte 14 Internal reference electrode 15 O-ring 21 Ion selective electrode 22 Shiobashi 23 Sample solution 24 Reference electrode 25 Electrometer 26 Saturated potassium chloride aqueous solution 27 Recorder

Claims (2)

[Claims] Claim 1: (A) General formula [1] {wherein, X represents either one or two long-chain hydrophobic groups, or one straight-chain hydrophobic group containing a rigid moiety in the chain; Y is a group selected from [Formula 1] (R3 is hydrogen or a methyl group, R
2 is a divalent group selected from -CO-, -COO-, -O- and -CONH-, n is an integer of 1 to 4, m is an integer of 1 or 2), R1 is hydrogen, methyl group, cyano group,
and a group selected from halogen atoms}, a linear polymer containing 50% by weight or more of units represented by }, and (B
) General formula [2] [Chemical formula 2] {where i represents an integer of 4 to 8, T represents a group selected from [Chemical formula 3], and U represents a group selected from [Chemical formula 4] or, T represents a group selected from [Chemical formula 5], and U represents a group selected from [Chemical formula 6]}. Molecular alignment film. 2. An anion-sensitive membrane comprising the composite molecular alignment membrane according to claim 1.