JPS62261951A - Selective ion permeable composition - Google Patents

Abstract

PURPOSE:To form a film which allows the selective permeation of specific ions at a specific temp. by subjecting a specific crown(thio) ether compd. to phase sepn. into a liquid crystal thereby forming a selective ion permeable compsn. CONSTITUTION:The selective ion permeable compsn. is formed by subjecting the crown(thio) ether compd. expressed by formula I to the phase sepn. into the liquid crystal and compounding said compd. therein. In formula, X is O or S, (p) is 2-8 integer, R<1> is CH3(CF2)qCH2CH3 (where q is 2-15 integer), R<2> is H, CH3(CF2)rCO (where r is 0-17 integer), or R<1> is CH3(CF2)s (where s is 0-17 integer), R<2> is CH3-R<3>-CO, R<3> is (CH2)t (t is 0-17 integer) or crown thioether expressed by phenylene. All of a nematic liquid crystal, smectic liquid crystal, and cholesteric liquid crystal are usable as the liquid crystal to be compounded with the compd. expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (6) Background of the Invention Technical Field The present invention relates to a novel selective ion permeable composition. To be more specific, there is a certain crown (
The present invention relates to a selective ion-permeable composition formed by phase-separating and blending a thio)ether compound.

Prior art biological membranes are composed of various phospholipids, cholesterols, proteins, etc., and fundamental functions such as permeability and selectivity are often associated with gel-liquid crystal transitions. Recently, a synthetic amphoteric substance having a hydrophobic group with two alkyl chains and an appropriate hydrophilic group in its molecule has been found to form oriented aggregates in water, and its phase diagram is very similar to that of natural phospholipids. It is also known that it is similar to Therefore, these are regarded as a new type of biological membrane model. In order to practically apply these new materials without losing their membrane-like functionality, suitable methods must be developed to polymerize or immobilize these materials in polymeric matrices. Composite membranes in which artificial lipids (or liquid crystal materials) are incorporated into polymeric matrices are useful because distinct changes in the thermal motion of thermal molecules that occur at the gel-liquid crystal phase transition temperature cause an increase in the water or gas permeability coefficient. , which can be applied to practical transmission control.

On the other hand, 1-dodecanoyl-10-carboxymethyl-,
10-Diaza-4. 7, 13. 16-tetraoxa-18-crown-6 (DCTO> is known as
This compound is 1,10-diaza-4. 7, 13.
It is also known to be synthesized from 16-tetraoxa-18-crown-6 [Bull.

Chem. Soc. Jpn. , 56, 559-5
63 (1983) Ko.

Polycarbonate/N-(4
-ethoxybenzylidene)-4-butylaniline (EB
BA) (40:60 weight ratio) was examined by differential scanning thermal analysis (DSC), and it was found that D
The SC peak is at 305, which corresponds to the crystalline-nematic liquid crystal phase transition of EBBA (TKN-304K>).

Therefore, this peak is not affected by the addition of DCTC (2.9 mol% relative to EBBA).

This is considered to be because DCT is uniformly dispersed in the film phase.

In addition, the measurement results of thermal control of potassium ion permeation are
For TC, NH+CHCOOH:NH CH2
PKal-3.45 in COO-, 〉NH CH2
COO- :> NHCH2 PK in COO-
, 1-6.99. For the transport of DCTC in liquid membrane systems, > NH2Co in the membrane phase with the help of anionic carboxylates.

- has been shown to effectively extract potassium ions, while >N)(CH2Coo- causes rapid release of potassium ions into the aqueous phase due to protonation of the cyclic nitrogen. Therefore, polycarbonate/ EBBA binary composite membrane does not permeate potassium ions.
A composite membrane containing dispersed DCTO allows potassium ions to permeate throughout the entire temperature range.

■． OBJECTS OF THE INVENTION It is therefore an object of the present invention to provide novel selectively ion permeable compositions. Another object of the invention is to
It is therefore necessary to provide a novel laundering ion permeable composition that can form a membrane that is selectively permeable to specific ions at specific temperatures.

These advantages are achieved by a selective ion-permeable composition comprising a crown (thio)ether compound represented by the general formula (2) mixed into a liquid crystal in a phase-separated manner.

[However, in the formula, X is O or S, p is an integer from 2 to 8,! FC (A) R'G; ECF3 (CF2
)q CH2 CH2 (however, q is an integer from 2 to 15 and i6>, R2 is H or CHs (CH2
), C.

(However, r is an integer from 0 to 17) or (B)
R1 tma CH3 (CH2 )s (However, S
is an integer from O to 17), R2 is CH3-R3-CO
[However, R3 is (CH2) t (However, t■
．． Detailed Description of the Invention The crown (thio)ether used in the present invention is a novel compound represented by the general formula (2).

In this general formula, X is O or o, p is an integer from 2 to 8, preferably 2 to 4, most preferably 3 to 4, and for R1a and R2:
CF2>qCH2CH2 (where q is an integer of 2 to 15, preferably 3 to 10, most preferably 5 to 8), R2 is H or CHs (CR2) r
CO (where r is an integer of O to 17, preferably O to
15, most preferably an integer from O to 10) or (B) R1 is CHs (CH2)S (where S
is an integer from 0 to 17, preferably from 5 to 17, most preferably from 7 to 15), R2 is CH3-R3-C
0 [However, R3 is (CH2)1 (however, t is O~1
An integer of 7, preferably 2 to 8, and most preferably representative poly(thio)ethers according to the present invention include:

CH3(CH2)2C=0 CH3(CH2) to C□0 CH3(CH2)2 C=0 CH3(CH2)2 C=0 CH3(CH2)2 C=0 Crown (thio)ether represented by general formula 1 The compound (provided that when R2 is H), that is, the compound of general formula (1), is a crown (thio)ether compound represented by general formula (1) (wherein, X, R+, and p are as described above). can be obtained by reacting with a hydrogenating agent.

Examples of hydrogenating agents include lithium, aluminum hydride, sodium aluminum hydride, potassium aluminum hydride, and sodium borohydride. The amount of the hydrogenating agent used per 1 mol of the compound of general formula (1) is 4 to 8 mol, preferably 6 to 7 mol. This reaction is carried out by dissolving the compound of general formula (1) and a hydrogenating agent in an anhydrous organic solvent, and dissolving the compound of general formula
It is carried out at a temperature of 80° C. for 2 to 6 hours, preferably 3 to 4 hours. Examples of organic solvents include dimethylformamide, dimethylsulfoxide, tetrahydrofuran, dioxane, diethyl ether, acetonitrile, and benzonitrile.

Therefore, the crown (thio) ether compound of the general formula (2) is an aminobenzo crown (thio) ether compound represented by the general formula (Vl (however, X and p are as described above)), and the crown (thio) ether compound of the general formula (2) is an aminobenzo crown (thio) ether compound represented by the general formula (Vl) (wherein, COY (VII) [wherein, R1 is (A> CF3 (CF2), C
H2CH2 (however, q is an integer of 2 to 15) or (B) CH3 (CH2>, (however, S is O to 17
is an integer). ] It can be obtained by condensation with an alkanoic acid halide represented by:

The condensation reaction is preferably carried out in an organic solvent in the presence of a halogenated scavenger in an atmosphere of an inert gas such as nitrogen, argon or helium at a temperature of 0 to 30°C, preferably 5 to 20°C for 1 to 5 hours. is carried out for 2 to 3 hours. The molar ratio of the compound of general formula Vl and the compound of general formula (1) used is 1:1 to 3, preferably 1:1 to 1.5. The concentration of the compound of general formula (2) is 4 to 10% by weight, preferably 5 to 8% by weight. The hydrogen halide scavenger is used in an amount of 1 to 30 equivalents, preferably 1.5 to 3 equivalents, relative to the hydrogen halide generated during the reaction.

A crown (thio)ether compound represented by general formula I (provided that R2 is not H), that is, general formula ■
The crown (thio) ether represented by the general formula ■ (However, X, R1 and p are as described above) is the crown (thio) ether represented by the general formula It is obtained by reacting and condensing with an alkanoic acid halide represented by (as described above).

The condensation reaction is carried out in a precipitated solvent in the presence of a hydrogen halide scavenger in an atmosphere of an inert gas such as nitrogen, argon, or helium at a temperature of 0 to 30°C, preferably 5 to 20°C.
The process is carried out for a period of time, preferably 2 to 3 hours. General formula II
The molar ratio of the compound I to the compound represented by general formula +V is 1:1 to 3, preferably 1:1 to 1.5. After the reaction, the precipitate was distilled off under reduced pressure, the residue was washed with acid, and washed with water.
Further recrystallization provides a highly pure product.

In any of the condensation reactions, the precipitating solvent includes dimethylformamide, dimethylsulfoxide, tetrahydrofuran, dioxane, diethyl ether, chloroform, carbon tetrachloride, trichloroethylene, acetonitrile, benzonitrile, and the like. In addition, examples of hydrogen halide scavengers include dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, butylamines, ethylenediamine, diethylenetriamine, hexamethylenediamine, pyridine, potassium carbonate, Examples include sodium carbonate.

The concentration of the crown (thio)ether not represented by the general formula (2) in such an organic solvent is 2 to 10% by weight, preferably 4 to 6% by weight. Further, the amount of the hydrogen halide scavenger in this case is 1 to 10 equivalents, preferably 2 to 4 equivalents, relative to the hydrogen halide generated during the reaction.

As the liquid crystal compound to which the crown (thio)ether represented by the general formula 1 is blended, any of the conventionally known nematic liquid crystals, smectic liquid crystals, and cholesteric liquid crystals can be used. Representative examples of nematic liquid crystals and smectic liquid crystals include 4-(4-ethoxybenzylidene)-4-hexylaniline, N-(4-butoxybenzylidene)-4-n-octyl-2-methylaniline,
N-(4-n-propoxybenzylidene)-4-〇-octylaniline, N-(a-n-hebutylbenzylidene)-4-cyanoaniline, N-(4-n-octylbenzylidene)-4-cyanoaniline , N-(4-cyanobenzylidene)-4-ethylaniline, N-(4-ethoxybenzylidene)-4-butylaniline, N-(4-methoxybenzylidene)-4-butanoyloxyaniline, N-(4- butanoyloxybenzylidene)-4-methoxyaniline, N-(4-methoxybenzylidene)-
4-(3-methylpentanoyloxy)aniline, N-
Azomethine series such as (4-n-hexyloxybenzylidene)-4-(5-methylhexanoyloxy)aniline, N-(4-n-butylbenzylidene)-4-β-cyanoethylaniline, n-butyl-4 -(4'-Butylphenylazo)-phenyl carbonate, azo or azoxy type such as 4-ethoxy-4'-n-hexanoyloxyazoxybenzene, 4-n-butylbenzoate-
4'-〇-hexyloxyphenyl ester, 4-n-
Ester systems such as hexyl carbonate-4'-pentoxyphenylbenzoate, 4,4'-jethoxy-
trans-stilbene, 4-ethoxy-2-methyl-4
Stilbenes such as '-n-butyl-trans-stilbene, 4-n-hexyl-4'-cyanobiphenyl, 4-
Biphenyl or terphenyl series such as n-propyl-4"-cyano-p-terphenyl, 4-(trans-4-
pentylcyclohexyl)benzonitrile, trans-
Transcyclohexane series such as 1,4-bis-(4-lopropoxycarbonyl)cyclohexane, 5-〇-hexyl-2-(4-hexyloxyphenyl)pyrimidine, 5-cyano-2-(4-〇- There are pyrimidine types such as hexylphenyl)pyrimidine. In addition, cholesteric liquid crystals include cholesteryl benzoate, 4-n-
dodecyloxy-1-naphthylidene cholesteryl-p-
Cholesterol derivatives such as aminobenzoate, N-(
Examples include 4-ethoxybenzylidene)-4-(2-methylbutyl)aniline and 4-ethoxy-4'-(2-methylbutyl mesogenic substances. Among these, azomethine is preferred.

The proportion of the crown (thio)ether represented by formula I to other liquid crystals is 0.1 to 40 parts by weight, preferably 1 to 15 parts by weight, per 100 parts by weight of other liquid crystals.

Normally, membranes supporting crown ethers allow specific ions to pass through, but such compositions undergo phase separation, as described below, and are dispersed in various polymer substrates, resulting in the formation of membranes. has the property of not transmitting specific ions, such as potassium ions, at a specific temperature, so this composition can be used as an ion-permeable membrane or a temperature control switch.

Next, the present invention will be explained in detail with reference to Examples.

Reference example 1 4'-aminobenzo-15-crown-5
Synthesized Pd/C0.32g was dampened with a small amount of water, ethanol was added and poured into a 200m eggplant-shaped flask, and then 4'-nitrobenzo-15-crown-53,1
5g (1,0OxlO-2 mol) in 100ml of ethanol
It was suspended and added. After reducing the pressure several times and thoroughly purging with hydrogen, the mixture was stirred at room temperature for 15 hours. At this time, the amount of hydrogen absorbed was about 700 m. (Theoretical amount: 670 d) Pd/C was removed by furnace, and the filtrate was distilled off under reduced pressure to obtain a pale yellow oil.

Reference example 2 4'-(N-2 "H, 2" II, 3H
Synthesis of ``,3''H-perfluoroundecanoylaminobenzo-15-crown-5 4'-Aminobenzo-obtained in Reference Example 1 was placed in a 200 d four-bottle flask equipped with a reflux condenser and a dropping funnel. 15-crown-5 (1.00X10-2 mol) and triethylamine 2.10 g (2.

08x10'mol) and dehydrated tetrahydrofuran (
Hereinafter referred to as THF, dissolved in >120m and 2H under a nitrogen stream.
．． 2H, 3H, 3H. - Perfluoroundecanoyl chloride 5.24G (1.07
The mixture was stirred at V temperature for 3 hours until the spot of the raw material crown ether disappeared by LC. The precipitate was filtered, the filtrate was distilled off under reduced pressure, and the residue was dissolved in chloroform.
) Washed with H~3 hydrochloric acid, washed with water, and solidified the chloroform phase under reduced pressure. This was dissolved in ethanol, treated with activated carbon, and then recrystallized from ethanol.

Yield 5. 27G, 71% yield Melting point = 129-130.5°C Infrared (IR) spectroscopy and NMR analysis of the product
As a result of the analysis, the results shown in Tables 1 and 2 were obtained, respectively.

1st IR (KBr method) 1665 Vc=0 1518 δNi1 Around 1200 V c-F l 1 4 5 Vc-o-c Table 2 MNR (Internal standard: TMS, solvent near, 55
S 1 h7, 24 S
1 G6, 76d 2
f, g4, 04 m 4
d3, 86 m 4
G3, 71 m 8 a, b2
, 54 t 4 i,j IR and NMR charts are shown in FIGS. 1 and 2, respectively.

Reference example 3 4'-(N-1"H, 1"H, 2"
H.

Synthesis of 2" H, 3" H, 3" H-perfluoroundecyl)-aminobenzo-15-crown-5 In a 500 rr 11 four-bottle flask equipped with a reflux condenser, 4'-(N-2" H , 2”
H, 3")!, 3"■-perfluoroundecanoyl)-aminobenzo-15-'77 pieces/- 5 3
．． Add OOQ (4.OOX10°3 mol) and dehydrate T.
Lithium aluminum hydride 1.0g (2.6x10-2mol
) and stirred under reflux for 4 hours. After cooling, water was added to decompose excess lithium aluminum hydride, the precipitate was filtered, and the filtrate was dried under reduced pressure. This was heated and dissolved in diethyl ether, treated with activated carbon, and then recrystallized from diethyl ether.

Yield: 1.21 (7, 41% yield; melting point: 282-84.05°C) IR and NMR analysis of the product gave the results shown in Tables 3 and 4, respectively.

3rd IR (KBr method) Absorption position (cm-1> Attribution 3330
VN-H 15186N-H around 1200 V c-F around 1130 v 166 from c-o-cIR
It was confirmed that the VC=O peak of the 5Cm'' amide disappeared.

Table 4 MNR (internal standard*: TMS, solvent 20DCfJ
+) δ(1)l)m) Fission Proton ratio Attribution 6.80 S 1 )e, h6.7
3 s 1 6.19 d 2 f, q4.
05 m 4 d3.88
m 4 G3.72 m
8 a, b3.14 t
2 i2.12 br
2 kl, 94 br 2
jIR and NMR charts are shown in FIGS. 3 and 4, respectively.

Reference example 4 4'-(N-butyryl) -4'
-(N-1" H, 1" H, 2" H, 2" H.

Synthesis of 3" H, 3" H-perfluoroundecyl)-aminobenzo-15-crown-5 In a four-hole flask with a capacity of 100, equipped with a reflux condenser and a dropping funnel, 4'-(N-1" H ,1”H.

2"H, 2"H, 3"H, 3"H-perfluoroundecyl)-aminobenzo-15-crown-50,
Add 81g (1,0x1 (13 mol)) and 0.2'l (2,1x10-3 mol) of triethylamine, and
Dissolved in HE20m, butyryl chloride 0 under nitrogen stream
．． 13Q (1,2xlO-3 mol) is dehydrated THE10
dl: Dissolved and added dropwise from the dropping funnel over 15 minutes. Thereafter, the mixture was stirred at room temperature for 3 hours. After filtering the precipitate, the filtrate was distilled off under reduced pressure, and the residue was dissolved in benzene, washed with I) H=3 hydrochloric acid, then washed with an aqueous solution of about 5 mmol/1 lithium hydroxide, then washed with water, and dissolved in benzene. The phases were concentrated under reduced pressure. Since there was not a single spot detected by small-sized TLC, it was purified by large-sized TLC. Using chloroform:methanol-25=1 as a developing solvent, a predetermined spot was collected, extracted with methanol, methanol was distilled off under reduced pressure, chloroform was added to remove the silica gel, and chloroform was distilled off under reduced pressure. When left to stand at room temperature, it crystallized.

Yield 0.49Cl, yield 50% Melting point: 56-58.0°C Regarding the product, IR,! > and NMR analysis, the results are shown in Tables 5 and 6, respectively.

Table 5 IR (KBr method) Absorption position (cm″1) Attribution 1650 Vc=07 Mito 1600.1
510 Vc=C aromatic around 1200
V C-F l 135 Vc-o-c Table 6 MN
R (internal standard: TMS, solvent = CD (jh) δ (ppm) R”a 2” Attribution 6.96
S 1 e6.82 d
1) f, g6.76 d 1 4.20 m 4 d4.0
0 m 4 c3.80
m 8 a, b3.70br2
h 2.04 br 2 jl, 9
6 t 2 il, 48
t 2 k1.24 m
2 NO, 80m 3
mIR and NMR charts are shown in Figures 5 and 6, respectively.

Reference example 5 4'-(N-acetyl) -4'
-(N-1"H, 1"H, 2"H, 2"H.

Synthesis of 3"H,3"H-perfluoroundecyl)-aminobenzo-15-crown-5 4°-(N-1"H,1
"H, 2" H, 2" H, 3" H, 3 "■-perfluoroundecyl)-aminobenzo-15-crown-
The above compound was synthesized by reacting 50,37q (5,0x10-4 mol) with acetyl chloride 0.058(J (7,4x10-' mol).Chloroform:methanol-25:1 was used as the developing solvent. there was.

Yield: 0.33 g, yield: 84%. The product was oily and did not crystallize. IR and NMR analyzes of the product were carried out and are shown in Tables 7 and 8, respectively.

Table 7 IR (neat> Absorption position <cm-') Attribution 1650
Vc=07mit'1585.1500
-Vc=C aromatic around 1200 V c-F l 120 Vc-o-c Table 8 MN
R (internal standard: TMS, solvent: 6.80 d
1 6.63d 1f・q 6.56 S 1 G4.0
8 m 4 d3.86
m 4 G3.69 m
8 a, b3.60 br
2 hl, 99 br
4 i, jl, 78 s 3
The kIR, fl and NMR charts are shown in FIGS. 7 and 8, respectively.

Reference example 5 4'-(N-dodecanoyl)-4'-
(N-1”H, 1”H, 2”)!, 2”H.

Synthesis of 3"H, 3"H-perfluoroundecyl>-aminobenzo-15-crown-5 4'-(N-1"H,
1”H, 2”? I, 2"H, 3")l, 3"H-
The above compound was synthesized by reacting 37 g (5,0XIO' mol) of 50° (perfluoroundecyl)-aminobenzo-15-crown-5 with 0.15 g (6,9 x 10-' mol) dodecanoyl chloride. Chloroform:methanol-30:1 was used as a developing solvent.

Yield: 0.32Q, yield: 69% The product was oily and did not crystallize. The results of IR and NMR analysis of the product are shown in Tables 9 and 10, respectively.

9th 1R (neat) Absorption position <crn-'> Attribution 1650
VC=O amide 1590.1510
Vc=C aromatic around 1200 V C-F l 120 Vc-o-c Table 10 M
NR (internal standard: TMS, solvent 2000 ρ3) δ (ppm) RH2 Attribution 6.84 d 1 6.66 d l ) f・G 6.57
S 1 G4.09 m
4 d3.92 m
4 G3.73m 8
a, b3.63 br 2
h2.01 br 2 jl
, 90 br 2 il, 50
br 2 kl, 20
m 18 fJO, 84t
3 mIR and NMR charts are shown in Figures 9 and 10, respectively.

Reference Example 7 Synthesis of 4'-(N-dodecanoyl)-aminobenzo-15-crown-5 Capacity 100 m1 equipped with reflux condenser and dropping funnel
4′-
Aminobenzo-15-crown-5 (5゜0X10'mol) and triethylamine 1.01C] (1,0O
10-2 mol of X was added and dissolved in 50 m of dehydrated THE. Dodecanoyl chloride 1.32g (6
,0Ox10-3 mol) was dissolved in 10m of dehydrated THE,
It was added dropwise in 15 minutes.

Thereafter, the mixture was stirred at air temperature for 4 hours. The precipitate was filtered and the filtrate was distilled off under reduced pressure. Dissolve the residue in chloroform and adjust to pH 3.
The mixture was washed with hydrochloric acid and water, and the chloroform phase was dried under reduced pressure. This was dissolved in ethanol, treated with activated carbon, and recrystallized from ethanol.

Yield 1.57Q, yield 67% Melting point: 108-110.0°C IR and NMR analysis of the product showed the results shown in Table 11.

Table 11 IR (KBr Law) Attribution 2920
vas )-cH2-2840VS 1655 Vc=0 amide 1140
The 11th chart of Vc-o-cIR
Shown in the figure.

Reference example 84°-(N-dodecyl)-aminobenzo-1
5-Crown-5 Synthesis reflux condenser and dropping funnel installed capacity 300rI
Into a four-loaf flask, 51.40 g of 4' (N-dodecanoyl)-aminobenzo-15-crown-
, 10 x 10' mol) and 15 Od of dehydrated THF were added thereto, 0.70 g (1.8 x 1O-2 mol) of lithium aluminum hydride was added under a nitrogen stream, and the mixture was stirred for 3.5 hours under continuous flow. After cooling, add water to decompose excess lithium aluminum hydride, filter the precipitate,
The filtrate was distilled off under reduced pressure. The residue was dissolved in chloroform and washed with water.

The chloroform phase was dried under reduced pressure, dissolved under heating in ether, treated with activated carbon, and then recrystallized from ether.

Yield @0.76C], yield 56% Melting point: 57-59.0°C IR and NMR analysis of the product gave the results shown in Tables 12 and 13, respectively.

Table 12 IR (K r method) Stem” Q Rainbow! ” Attribution 2918
Vas -cH2-2825Vs 1130 Vc-o-cH% 10.
06 9.86-0.20Q% 69.13
69.15 +0.02N% 3.10 2.
81 -0.29 IR confirmed the disappearance of the amide VC=O peak at 1655 cm-'. Further, an IR chart is shown in FIG.

Reference example Synthesis of 94°-(dobutyryl)-4'-(N-dodecyl)-aminobenzo-15-crown-5 Capacity 100Id with reflux condenser and dropping funnel attached
4'-(N-dodecyl)-aminobenzo 15-crown-50,70G (1°5
x 10'mol) and triethylamine 0.32a (
3.2×10 −3 mol) was dissolved in 30 ml of dehydrated THF. Butyryl chloride 0.200 under nitrogen stream
(1,9×10'mol) was dissolved in dehydrated THF10IIIi and added dropwise from the dropping funnel over 15 minutes. Thereafter, the mixture was stirred at room temperature for 2.5 hours. The precipitate was filtered and the filtrate was distilled off under reduced pressure. The residue was dissolved in chloroform, washed with pH-3 hydrochloric acid, washed with about 5 mmol/1 aqueous lithium hydroxide solution, and then washed with water. The chloroform phase was compressed under reduced pressure. Since there was not a single spot detected by small-sized TLC, it was purified by large-sized TLC. Using chloroform as a developing solvent, a designated spot was taken and extracted with methanol, the methanol was distilled off under reduced pressure, chloroform was added to the residue, the silica gel was removed, and the chloroform phase was distilled off under reduced pressure, but no crystallization occurred. The result was a light brown oil.

Yield: 0.39 g, yield: 75% The product was subjected to IR and NMR analysis, and the results shown in Tables 14, 15, and 16 were obtained, respectively.

Table 14 IR (neat> Absorption position (cm″1) Attribution 1650 Vc=o 7mit 1130
Vc-o-c Table 15 MNR (internal standard: TMS, solvent: <co and; n) -1111111 δ (ppm) j70 upward Assignment 6.92 d 1 6.82 d l) f・q 6.74 S 1 e4.2
0 m 4 d4, OOm
4. C 3.85m 8a, b3.60b
r2 h 2.04 t 2 kl, 5
4 br 2 full, 2em
20 +0.86t
6 j, m8% 9.87 9.
85-0.03G% 69.05 68.74-0.
31N% 2.68 2.72 +0.04I
R and NMR charts are shown in Figures 13 and 14, respectively.

Reference example 10 4°-(N-dodecyl)-4°-(N
Synthesis of -p-toluenesulfonyl)-aminoberezo-15-crown-5 In a 100 d capacity four-bottle flask equipped with a reflux condenser and a dropping funnel, 4'(N-dodecyl)-aminobenzo-15-crown-50,41CI (9゜0X10
-4 mol), triethylamine 0.30Cl (3,0X
10-3 mol) and toluenesulfonyl chloride 0.
Add 21CI (1,1x10°3 mol) and dehydrate TH.
It was dissolved in F25rIJi and stirred under a nitrogen stream for 29 hours. After cooling, the precipitate was filtered, and the filtrate was distilled off under reduced pressure. The residue was dissolved in chloroform, washed with DI-1-3 hydrochloric acid, and then with water, and the chloroform phase was distilled off under reduced pressure. However, since there was not a single spot detected by small-sized TLC, it was purified by large-sized TLG. Using chloroform:methanol=20:1 as a developing solvent, a predetermined spot was extracted and extracted with methanol, the methanol was distilled off under reduced pressure, chloroform was added to the residue, the silica gel was removed, and the chloroform phase was distilled off under reduced pressure. The remaining oil was heated and dissolved in petroleum ether, treated with activated carbon, and crystallized from petroleum ether.

Yield: 0.21 g, Yield: 37% Melting point: 71-72.5°C IR and NMR analysis of the product gave the results shown in Tables 17, 18 and 19, respectively.

Table 17 IR(KBr method)
Vas )-CHz-2840Vs 1340 Vas 302115
5 Vs=.

1140 Vc-o-c Table 18
MNR (internal standard: TMS, solvent near, 32d
2k, N7.04d
2 m, n6.64 d l
) f, Q6.52 d 1 6.40 s 1 e4, O
, Om 4 d3.80 m
, 4 c3.64m
8 a, b3.36 br 2
h2.32 S 3
.

1.16 m2Or o, 82t3jH%
8.50 8.55 +0.05C% 69.
41 65.05-0.36N% 2.31
2.35 +0.04 IR and NMR charts are shown in Figures 15 and 16, respectively.

Reference example゛ 11 4°-(N-dodecyl)-4'-(
Synthesis of N-toluoyl)-aminobenzo-15-crown-5 Synthesis of toluoyl chloride 4.08 g (3,0Ox10°2 mol) of p-toluic acid
and thionyl chloride 10rd were placed in a pear-shaped flask and heated under reflux for 3 hours. After cooling, excess thionyl chloride was distilled off by atmospheric distillation. 130-b was obtained by vacuum distillation.

Yield: 3.71, yield: 80% The product was subjected to IR and NMR analysis, and the results shown in Table 20 were obtained.

20 IR (neat) Absorption position (cm”) Attribution 1760) Vc=o acid chloride 815
A chart of 6C-H aromatic para-substituted IR is shown in FIG.

4'-(N-dodecyl)-4'-(N-toluoyl)-
Synthesis of aminobenzo-15-crown-5 4-(N-dodecyl)-
Monoaminobenzo 15-crown-50,32g (7°0x10°4 mol) and triethylamine 0.15G
(1,4x10-3 mol) and dehydrated THF15d
dissolved in After nitrogen substitution, toluoyl chloride 0.1
3CJ (8,4xlO-4 mol) was dissolved in 5d dry THF and added. The mixture was stirred at air temperature for 2 hours. Post-treatment was carried out in the same manner as in the case of toluoyl chloride. It did not crystallize and became an oily substance. It was developed using chloroform:methanol=30:1 as a developing solvent.

Yield: 0.24 CI, yield: 60% The product was subjected to IR, NMR, and elemental analysis, and the results shown in Tables 21, 22, and 23 were obtained, respectively.

21st IR (neat> Absorption position (cm”> Attribution 1640 Vc=07mit 1590.1
505 Vc=C aromatic 1140
VC-0-C8256C-H Aromatic para-substitution Table 22 MNR (internal standard: TMS, solvent: CDCN
:+) δ(1)pm) jl'' Attribution 7.07 d 2 k,, 26
．． 84 d 2 m, m6.
56 6 1) f, C16,50d
1 6.42 S 1 C
3,98m 4 d3.78
m 4 c3.63
m 8 a, b3.60
br 2 h2.16
S 3 01.16 m
20io, 80br
3jIR and NMR charts are shown in Figures 18 and 19, respectively.

Example 1 Preparation of polymer composite membrane Polycarbonate < P C) /N-(4-ethoxybenzylidene)-4-butylaniline (EBBA) = 4
0:60 (weight ratio), EBBA/crown ether=
1,2- as a solvent so that the molar ratio was 70:3.
Dichloroethane was used and mixed, and a film was prepared by a glass surface casting method.

Example 2 Differential scanning thermal analysis (DSC) measurement example 1
DSC measurement was performed on the film obtained in . As the crown ether, crown ethers having a fluorocarbon chain (Reference Example 4), (Reference Example 5), (Reference Example 6), (Reference Example 9), (Reference Example 10) and (Reference Example 11) were used. . The compounds of Reference Example 5 and Reference Example 10 are shown in FIG. 20 together with the DSC measurement results of only crown ether. From this, in the system of crown ether (Reference Example 5) having a fluorocarbon chain, at 339K, Reference Example 5
A peak corresponding to the melting point of the compound was observed, confirming that there was phase separation in the membrane. When the ΔH was determined, it was 16.4 kca 11 mol in the case of only the compound of Reference Example 5, and 11 mol kca at 5°26 in the membrane. In the system of the compound of Reference Example 10, only absorption due to the phase transition of 305Kl:EBBA was observed, and it was considered that the system was uniformly dispersed.

Example 3 Metal ion transport experiment (A> Passive transport using benzo-15-crown-5 having a fluorocarbon chain as an ionophore) The transport conditions are shown in Table 24.

Table 24 Transport conditions TN phase 30m1 OUT phase 30d The results of the transport experiment are shown in Tables 25, 26 and 27 for each compound of Reference Examples 5 and 6, respectively. Figure 21 shows the results plotted against each other. In addition, the Arrhenius plot is shown in Fig. 22, and from this it can be seen that the activation energy Ea, the logarithm of the frequency factor 10CIA
The results are shown in Table 28. In addition, Ea and 10(J
A is the slope and intercept of the straight line in the Arrhenius plot.

Table 28 Ea and Hi 1o (IA Reference example 4 186 23.4 Reference example 5
197 25.3 Reference example 6
121 20.9 (B) Has a fluorocarbon chain. Ionophage of benzo-15-crown-5? −
Reference Example 4, which was confirmed to undergo phase separation in the membrane by DSC measurement, was used as the CS + passively transported raw ether used as the sample. Transport conditions are shown in Table 29.

Table 29 Transport conditions The first 10 hours were left at 10"C as an induction period, and the EB
10°C, 20"lJ above the Tc of BA [40"lJ at 2 hour intervals at 40'C and 50'C above the TC.
Sample 200 μm each from the OUT phase, and 3 m of water
The CS concentration was determined by atomic absorption spectrometry. The permeation rate V was determined from the determined concentration change and is shown in Table 30. No CS transport occurred above the Tc of EBBA, and transport occurred only above the Tc. This is because in this yarn, the crown ether phase separates in the membrane, so C3
1 in a 2:1 sandwich structure, which is why it is thought to have been transported.

Table 30 'S Jurin/Upper Liang (C) Ionophore of benzo-15-crown-5 with fluorocarbon chain? - Is the polymer composite membrane used as an on-off switch experiment as an ionophore? A film was produced in the same manner as in Example 1 using the compound of Reference Example 4 as -.

The transportation conditions are the same as in Example 3(A). The first 10 hours were left at 10°C as an induction period, then 6 hours from the start of sampling at 10°C, the next 5 hours at 40°C, the next 12 hours at 10°C, and roughly the next 4 hours at 40°C. did. Sampling was carried out at 10'C at 2 hour intervals, and at 40'C at 1 hour intervals at 100 μΩ each from the OUT phase.
Diluted in ml. The K concentration determined by atomic absorption spectrometry was converted to the concentration in the OUT phase cell and is shown in Table 31. The K concentration was also plotted against time and is shown in FIG.

Table 32 On-off switch experimental results Transport temperature
Transportation time [K+] x 104 ('C) (
h> (M)□ 10 17 0.31018 0
．． 527 19 0.682 20 1.49 21 2.02 10 23 3.57 25 5.98 27 6.82 29 6.70 31 7.19 33 7.32 Continued on next page (continued) Transport temperature Transport time [K]X104('C)
(t-1>(M>40
34 10.2 35 9.5B 36 12.9 37 16.3 (C) K using comparative compound as ionopher Crown ether as passive transport ionopher (Reference Example 9), (
Using Reference Example 10) and (Reference Example 11), Example 3 (
The same procedure as A) was carried out. The results are shown in Tables 33, 34 and 35, respectively. Further, the transmittance Pk is plotted against temperature and shown in FIG.

These results are Arrhenius plotted and shown in Fig. 25, and from this the activation energy Ea and the logarithm of the H degree factor 10
(+A was determined and shown in Table 36.

Table 36 Ea and log A Reference example 9 34.4 42.2 -3.16-1
．． 74 Reference Example 10 45.1 105 -1.3
9 9.72 Reference Example 11 45.6 97.4
-1.38 7.38 (D) Ionophore the comparative compound? C used as - Crown ether (Reference Example 10) was used as a passive transport ionopher. This system was confirmed to be uniformly dispersed by DSC measurement. The measurement method was the same as in Example 3(B). As a result, no transport took place. This is considered to be because the compound of Reference Example 10 was uniformly dispersed in the film, and therefore C3 could not be taken in by the Sano-Ditch structure.

IV. Specific Effects of the Invention The selective ion-permeable composition according to the present invention is formed by blending the crown (thio) ether compound represented by the general formula (2) into a liquid crystal in a phase-separated manner. For example, a membrane formed by dispersing this in a polymer gas has the property of not transmitting specific ions such as potassium ions at all at a specific temperature, but rapidly transmitting these ions when the temperature exceeds a predetermined temperature. This composition can be used as an ion permeable membrane, a temperature control switch or a sensor.

[Brief explanation of drawings]

Figure 1, Figure 3, Figure 5, Figure 7, Figure 9, Figure 11,
Figures 12, 13, 15, 17 and 18
The figure is an infrared (IR) spectroscopic analysis chart of the crown (thio)ether compound used in the present invention, Figure 2.
Figure 4, Figure 6, Figure 8, Figure 10, Figure 14, Figure 16
Figures 17 and 19 are NMR analysis charts of the crown (thio) ether compound used in the present invention, and Figure 20 is the DS of the crown (thio) ether compound.
C graph, Figures 21, 23 and 24 are Rk
FIG. 22 and FIG. 25 are graphs showing Arrhenius plots. Patent Applicant: Chiru Seven Co., Ltd. 1st Cause 2nd Issue 3rd Figure 4 Figure 5 6th Cause 7th Figure 9 Decoy Figure 10 Figure 11 Figure 12 Figure 13 Figure 15 Figure 16 Figure 17 Figure 18 昂T/にT/に3.2 3.3 (1/T) ni-'

Claims (3)

[Claims] (1) A selective ion-permeable composition comprising a phase-separated crown (thio)ether compound represented by the general formula I incorporated into a liquid crystal. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [However, in the formula, X is 0 or S, p is an integer from 2 to 8, and (A) R^1 is CF_3 (CF_2)_qC
H_2CH_2 (q is an integer from 2 to 15)
, R^2 is H or CH_3(CH_2)_rCO (where r is an integer from 0 to 17) or (B) R^1
is CH_3(CH_2)_s (where s is an integer from 0 to 17), R^2 is CH_3-R^3-CO [where R^3 is (CH_2)_t (where t is an integer from 0 to 17)
) or phenylene] or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. A crown (thio)ether compound represented by ]. (2) The composition according to claim 1, wherein P is an integer of 2 to 8. (3) The composition according to claim 1 or 2, wherein X is 0.