JPH05214330A - Mixture composed of ionic complex with medium - Google Patents

Abstract

PURPOSE:To obtain the subject mixture of an ionic complex (which can also be called a molecular complex) having a long-lived charge separated state with a medium. CONSTITUTION:The objective mixture comprises an ionic complex composed of an amphiphatic polyelectrolyte (1a) having a 'micro-phase separated state in which an aggregated phase of hydrophobic groups (1a1) partially containing an electron donative hydrophobic group (D) is wrapped in hydrophilic groups' and a surfactant (1b) and an electron acceptor (1c1) or an electron accepting surfactant or a combination thereof bound to the outside thereof with a nonpolar medium. Thereby, a long-lived charge separated state is realized.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a mixture of an ion complex (also called a molecular complex) and a medium.

[0002]

2. Description of the Related Art Recently, amphiphilic polyelectrolytes have been attracting attention. Needless to say, the amphipathic polymer electrolyte is a generic term for polymers having both a hydrophobic group and a hydrophilic group, and the polymer known as polysoap from a long time ago belongs to this group. Polymers of this type were initially only shown to be interesting as polymers that behave similarly to low molecular weight surfactants. However, as the three-dimensional structures of natural globular proteins have been elucidated one after another, amphiphilic polyelectrolytes have been attracting attention from the viewpoint of physicochemical models similar to the morphology and function of biopolymers. There is.

The most characteristic property of the amphipathic polyelectrolyte is that in an aqueous solution, hydrophobic groups self-associate in the molecule to form microdomains (aggregated phases), and the surroundings thereof are charged segments (hydrophilic groups). ) Surrounds and forms a micellar structure (microphase separation structure). The interaction of hydrophobic groups that causes self-association is based on the unique liquid structure of water as a solvent, not on the direct attractive interaction between hydrophobic groups, and the structural change of water is It occurs by contributing to stabilization. The water in the first layer, which is in contact with the hydrophobic group of the amphiphilic polyelectrolyte dissolved in water, forms a regular structure, and the hydrophobic group is clathrated by ice-like clusters, It undergoes so-called hydrophobic hydration. When the hydrophobic groups in such a state associate with each other, a part of the ordered structure water is normally released to the water state. At this time, the entropy of the whole system increases, the free energy decreases, and it changes toward stabilization.

Such interaction-based association of hydrophobic groups occurs in competition with repulsion between charges of segments. Since the association of hydrophobic groups is affected by the degree of ionization of the electrolyte segment, in the case of the amphipathic polymer carboxylic acid, the transition of the molecular morphology may be induced by the pH change.
This phenomenon is of interest in relation to pH denaturation of proteins and helix-coil transition of polypeptides.

In this case, in the low dissociation state, the molecules have a compact structure due to the association of the hydrophobic groups.
), As the degree of dissociation increases, the repulsion between segment charges surpasses the interaction of hydrophobic groups, resulting in an extended structure. Since this change is a cooperative phenomenon, it occurs sharply within a narrow range of dissociation and can usually be seen as a transition between two states.

In addition, the strength of the acid or base located in the immediate vicinity of the hydrophobic group is affected by the hydrophobic field (aggregation phase).
For example, in a protein molecule, a carboxyl group surrounded by hydrophobic amino acid residues has a regular structure of water around it, which hinders hydration of H ⁺ ions and thus suppresses dissociation. It is known that the acidity is weakened.

Since the local dielectric constant is reduced around the hydrophobic group, ionic bonds and hydrogen bonds are strengthened in a hydrophobic environment, and when these bonds and hydrophobic bonds work at the same time, they are cooperative with each other. Is brought about. The dense structure of the amphipathic polyelectrolyte shows a phenomenon in which a hydrophobic low-molecular-weight substrate is incorporated into the hydrophobic part to be solubilized in water. This phenomenon is of interest from the standpoint of model research in relation to the phenomenon that a natural enzyme protein incorporates a substrate into a hydrophobic region and the phenomenon that DNA specifically incorporates a polycyclic aromatic compound.

Further, the microphase-separated structure of the amphipathic polyelectrolyte provides a new possibility for an optical functional material aiming at spatially separating photoexcited electrons. For example, when a molecule or organic group (donor) that donates electrons by photoexcitation is made hydrophobic and a molecule or organic group (acceptor) that receives electrons is made hydrophilic, the donor-acceptor is defined as a hydrophobic domain (aggregated phase) -hydrophilic domain. Dispersed efficiently (outside the aggregation phase). At this time, by changing the structure of the amphipathic polyelectrolyte, it is possible to arbitrarily change the distance between the donor-acceptor and the energy level difference between the highest occupied molecular orbital of the donor and the lowest unoccupied molecular orbital of the acceptor to some extent. It is possible. As a result, improvement in charge separation efficiency due to photoexcitation can be expected. Furthermore, the high packing density of hydrophobic domains (aggregated phase) is effective for optical memory materials having high structure sensitivity such as PHB memory.

The inventors of the present invention have previously used anionic 2-acrylamido-2- as a base monomer that gives an electrolyte.
Methylpropanesulfonic acid (2-Acrylamido-2- Methylpr
Copolymerization was performed using opansulfonic acid (abbreviation: AMPS) to synthesize various amphiphilic polyelectrolytes. And
For these series of polyelectrolytes, aqueous solution viscosity, surface tension, NMR spectrum, cast film morphology,
We have studied in detail the incorporation of hydrophobic low molecular weight substrates by fluorescent probe method and equilibrium dialysis method.

The polyelectrolyte obtained from AMPS is a kind of sulfonic acid salt. Since this sulfonic acid is a strong acid, this polyelectrolyte is usually in a state of total dissociation in an aqueous solution. In that state, strong electrostatic repulsion between charged segments is always working. However, when the content of the hydrophobic group becomes high, this is surpassed, and intramolecular association of the hydrophobic group becomes possible to form a dense structure. In particular, NMR and the like suggested that aromatic hydrophobic groups have a high packing density as a result of intramolecular self-association in water.
On the other hand, it was suggested that the aliphatic hydrophobic group forms a relatively loose association (low packing density).

In addition, the amphiphilic polyelectrolyte lowers the surface tension of the aqueous solution. The higher the content of the hydrophobic group in the polymer, the greater the surface active effect. Interestingly, not only the content, but also the type of hydrophobic group gives different surface-active effects. Aromatic hydrophobic groups have a more pronounced surface-active effect than aliphatic groups. Further, the larger ring pyrenyl group is more effective than the phenanthryl group.

As a reference, Polymer J., 21 , 267-274
(1989), J. Phys. Chem., 93 , 1643-1648 (1989), Ma
cromolecules, 21 , 101-107 (1988), J. Polym. Sci. P
olym. Lett. Ed., 21 ,, 167-170 (1983). By the way, conventional amphiphilic polyelectrolytes having a "microphase-separated structure in which a hydrophilic group wraps around a cohesive layer of hydrophobic groups" have an expression of the above-mentioned specific properties only in an aqueous solution. It is possible, and there is a problem that the range of use or application is significantly limited.

Therefore, it is possible to dissolve the amphiphilic polyelectrolyte in a hydrophobic substance such as a hydrophobic organic substance or plastics while retaining its specific structure. An ion complex that can achieve a long-lived charge separation state between a donor (donor) and an electron acceptor (acceptor) was proposed (Japanese Patent Application No. 3-22).
5939).

FIG. 1 and FIG. 2 schematically show the molecular structure of such an ion complex. The ion complex (1) has an “electron-donating hydrophobic group (donor; D).
With a hydrophilic group surrounding the aggregated phase of the hydrophobic group (1a ₁ ) containing a part of "an amphiphilic polyelectrolyte (1a)" and an interface bonded to the outside. It is composed of an activator (1b) and an electron acceptor (1c ₁ ), or those obtained by adding an electron-accepting surfactant (1c ₂ ). When a light having a wavelength excited by a donor is applied to this ion complex, a long-life charge separation state is realized.

The reason for this is not entirely clear, but it can be considered as follows. In the ion complex (1), the donor is protected from the external environment by being chemically bound to the amphiphilic polyelectrolyte itself and confined in the aggregation phase of other hydrophobic groups. In addition, the acceptor is fixed to the periphery of the aggregation phase in a concentrated form by being chemically bonded or mixed with the amphipathic polymer electrolyte itself. Since the surface active agent and the electron-accepting surface active agent extend the hydrophobic group toward the outside, the surface of the ion complex is considered to be covered with a large part of the hydrophobic group of the surface active agent. .. Therefore, this ion complex can be dissolved (dispersed) in an organic solvent or a hydrophobic substance (plastic molded product) while maintaining its unique structure (micro phase separation structure), and it is a transparent solution or plastic. It is presumed that it can be uniformly dispersed in a molded product such as a plastic lens substrate without impairing transparency.

Furthermore, due to its unique structure (microphase separation structure), the donor is surrounded by other excess hydrophobic groups (1a ₁ ), and the electron acceptor (1c ₁ ) or electron accepting interface There is a slight distance from the activator (1c ₂ ). When such a system is irradiated with light, the donor is excited and its electron moves to the electron-accepting group (acceptor; A) of the electron acceptor (1c ₁ ) or the electron-accepting surfactant (1c ₂ ). Cause

[0017] As a result, ion radicals · D ⁺ and · A ⁻ are generated to generate a charge separation state.

[0018] Since generally the electron transfer reaction in the molecule very fast, · A ^- faster reverse electron transfer to · D ⁺ from, as a result the lifetime of the charge-separated state is extremely short, usually not observed is there. In contrast, the donor and acceptor of the ion complex shown in FIGS. 1 and 2 are
In addition to the fact that the distance between them is separated by the hydrophobic aggregation phase, the charge separation state is stabilized by the interaction between the acceptors, and as a result, it is considered that the long-life charge separation state is expressed. Be done.

[0019]

However, even in the ion complex as shown in FIGS. 1 and 2,
The life of the charge separation state was not yet sufficient. Therefore,
An object of the present invention is to prolong the life of the charge separation state of the ion complex.

[0020]

The present inventors have suspected that the medium surrounding the ion complex may contribute to the life of the charge separation state. And as a result of research,
It was found that the life of the charge-separated state increases when the medium is non-polar, and the present invention has been completed. Therefore, the present invention provides a mixture of an ion complex and a medium, wherein the ion complex is a "microphase in which a hydrophilic group wraps around an aggregated phase of a hydrophobic group partially containing an electron-donating hydrophobic group. An amphiphilic polyelectrolyte (1a) having a `` separation structure '' and a surfactant (1b) and an electron acceptor (1c ₁ ) or an electron-accepting surfactant (1c ₂ ) or an electron bound to the outside thereof. The acceptor (1c ₁ ) and the electron-accepting surfactant (1c ₂ ) or the surfactant (1b), the electron acceptor (1c ₁ ) and the electron-accepting surfactant (1c ₂ ) A mixture characterized by being polar is provided.

[0021]

First, the ion complex used in the present invention will be described. As shown in FIGS. 1 and 2 (conceptual diagram), the ion complex used in the present invention comprises an amphipathic polymer electrolyte (1a) having a microphase-separated structure and an interface ionically bonded to the outside thereof. Activator (1b) and electron acceptor (1
c ₁ ) or an electron-accepting surfactant (1c ₂ ), or a combination thereof.

The surfactant, the electron acceptor and the electron accepting surfactant are not limited to a single substance, and two or more kinds may be mixed and used. Further, the electron acceptor (1c ₁ ) is not limited to being used alone as shown in FIG. 1, but as shown in FIG.
The electron-accepting surfactant (1c ₂ ) may be used simultaneously, and similarly, the surfactant (1b) is not limited to being used alone,
You may use together with an electron-accepting surfactant (1c ₂ ).

First, one of the ion complexes of the present invention
Specific explanation of the amphiphilic polyelectrolyte that forms part
To do. A typical amphipathic polyelectrolyte is shown in FIG.
It is a copolymer having the structure of general formula (I). Copolymer content
The offspring is generally around 10,000 to 300,000. General formula
In (I), R₁, R₂, R₃Is H or CH₃And
R, Y₁, Y₃Is O or N-H or N-CH₃And
Y₂Is N-H or N-A_Four (A_FourIs C ₁~ C₁₈A
Rukiru group), and A₁Is C₂~ C_FourAlkylene group
And A ₂Is C which may contain an aromatic ring₆~ C
₁₈Is a hydrocarbon residue of₃Anthracene, h
Enanthrene, pyrene, phthalocyanine, metal phthalocyanine
A residue of anine, porphine or metalloporphin,
M is Na or K.

Further, x, y, z represent copolymer composition ratios, and x + y + z = 100. In this, y is 10 to 70
It is preferably 40 to 60, and z is 0 to 5 and preferably 0.05.
~ 3. The copolymer represented by the general formula (I) includes the monomer represented by the general formula (II) shown in FIG. 5 and the general formula (II) shown in FIG.
It is obtained by copolymerizing the monomer of I) and the monomer of general formula (IV) shown in FIG. 7 and then neutralizing with an alkali.

R in the general formula (II)₁, Y₁, A₁,
R in the general formula (III)₂, Y₂, A ₂And general formula (IV)
R in₃, Y₃, A₃Has the same meaning as in formula (I).
It Examples of the monomer of the general formula (II) include 3-a
Cryloyloxypropane sulfonic acid, 3-methacryloyl
Iloxypropanesulfonic acid, 2-acrylamide-
2-Methylpropanesulfonic acid (AMPS), 2-methacrylate
Lamido-2-methylpropanesulfonic acid, etc.
It

Examples of the monomer of the general formula (III) include cyclohexyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylamide, cyclohexyl methacrylamide, N-cyclohexyl-N-methyl acrylamide, N-cyclohexyl-N-methyl methacrylamide, cyclohexyl methyl acrylate. , Cyclohexylmethylmethacrylate, cyclohexylmethylacrylamide, cyclohexylmethylmethacrylamide, N-cyclohexylmethyl-N-methylacrylamide, N-cyclohexylmethyl-N-methylmethacrylamide, phenylacrylate, phenylmethacrylate, phenylacrylamide, phenylmethacrylamide, N- Methyl-N-phenylacrylamide, N-methyl-N -Phenyl methacrylamide, benzyl acrylate, benzyl methacrylate, benzyl acrylamide, benzyl methacrylamide, N-benzyl-N-methyl acrylamide, N-benzyl-N
-Methyl methacrylamide, 1-norbornyl acrylate, 1-norbornyl methacrylate, 1-norbornyl acrylamide, 1-norbornyl methacrylamide, N-methyl-N- (1-norbornyl) acrylamide, N-methyl -N- (1-norbornyl) methacrylamide, cyclooctyl acrylate, cyclooctyl methacrylate, cyclooctyl acrylamide, cyclooctyl methacrylamide, N-cyclooctyl-
N-methyl acrylamide, N-cyclooctyl-N-
Methyl methacrylamide, adamantyl acrylate,
Adamantyl methacrylate, adamantyl acrylamide, adamantyl methacrylamide, N-adamantyl-N-methyl acrylamide, N-adamantyl-N
-Methyl methacrylamide, 1-naphthyl acrylate, 1-naphthyl methacrylate, 1-naphthyl acrylamide, 1-naphthyl methacrylamide, N-methyl-N- (1-naphthyl) acrylamide, N-methyl-
N- (1-naphthyl) methacrylamide, 2-naphthyl acrylate, 2-naphthyl methacrylate, 2-naphthylacrylamide, 2-naphthylmethacrylamide,
N-methyl-N- (2-naphthyl) acrylamide, N
-Methyl-N- (2-naphthyl) methacrylamide, n
-Dodecyl acrylate, n-dodecyl methacrylate, n-dodecyl acrylamide, n-dodecyl methacrylamide, Nn-dodecyl-N-methyl acrylamide, Nn-dodecyl-N-methyl methacrylamide, cyclododecyl acrylate, cyclododecyl methacrylate , Cyclododecyl acrylamide, cyclododecyl methacrylamide, N-cyclododecyl-N-methyl acrylamide, N-cyclododecyl-N-methyl methacrylamide, n-hexadecyl acrylate, n
-Hexadecyl methacrylate, n-hexadecyl acrylamide, n-hexadecyl methacrylamide, N-
n-hexadecyl-N-methylacrylamide, Nn
-Hexadecyl-N-methylmethacrylamide, n-octadecylacrylate, n-octadecylmethacrylate, n-octadecylacrylamide, n-octadecylmethacrylamide, Nn-octadecyl-N-methylacrylamide, Nn-octadecyl-N-methyl Methacrylamide, di-n-octyl acrylamide, di-n-octyl methacrylamide, di-n-decyl acrylamide, di-n-decyl methacrylamide,
Examples thereof include di-n-dodecyl acrylamide and di-n-dodecyl methacrylamide.

Examples of the monomer of the general formula (IV) include 9-anthracene methyl acrylate, 9-anthracene methyl methacrylate, 9-anthracene methyl acrylamide, 9-anthracene methyl methacrylamide, 9-phenanthrene methyl acrylate and 9-phenanthrene. Methyl methacrylate, 9-phenanthrene methyl acrylamide, 9-phenanthrene methyl methacrylamide, N-methyl-N- (9-phenanthrene methyl) acrylamide, N-methyl-N- (9-phenanthrene methyl) methacrylamide, 1-pyrene methyl acrylate , 1-pyrenemethylmethacrylate,
1-pyrenemethylacrylamide, 1-pyrenemethylmethacrylamide, N-methyl-N- (1-pyrenemethyl) acrylamide, N-methyl-N- (1-pyrenemethyl) methacrylamide, 4-acryloyloxymethylphthalocyanine and its magnesium or Manganese or iron or copper or zinc complex, 4-methacryloyloxymethyl phthalocyanine and its magnesium or manganese or iron or copper or zinc complex, 4-acrylamidomethyl phthalocyanine and its magnesium or manganese or iron or copper or zinc complex, 4-methacrylamide Methylphthalocyanine and its magnesium or manganese or iron or copper or zinc complex, N-methyl-4-acrylamidomethylphthalocyanine and its magnesium or manganese or iron or copper or Lead complex, N- methyl-4-methacrylamide-methyl phthalocyanine and its magnesium or manganese or iron or copper or zinc complexes, 5- (4'-
Acryloyloxymethyl) phenyl-21H, 23H-porphine and its magnesium or manganese or zinc or iron (III) chloride or yttrium or erbium or europium complex, 5- (4'-methacryloyloxymethyl) phenyl-21H, 23H-porphine and Its magnesium or manganese or zinc or iron (III) chloride or yttrium or erbium or europium complex,
5- (4'-acrylamidomethyl) phenyl-21H,
23H-porphine and its magnesium or manganese or zinc or iron (III) chloride or yttrium or erbium or europium complex, 5- (4'-methacrylamidomethyl) phenyl-21H, 23H-porphine and its magnesium or manganese or zinc or chloride Iron (III
) Or yttrium or erbium or europium complex, 5- (4'-acryloyloxymethyl) phenyl-10,15,20-triphenyl-21H, 23H-porphine and its magnesium or manganese or zinc or iron (III) chloride or yttrium Or erbium or europium complex, 5- (4'-methacryloyloxymethyl)
Phenyl-10,15,20-triphenyl-21H, 23H-porphine and its magnesium or manganese or zinc or iron (III) chloride or yttrium or erbium or europium complex, 5- (4'-acrylamidomethyl)
Phenyl-10,15,20-triphenyl-21H, 23H-porphine and its magnesium or manganese or zinc or iron (III) chloride or yttrium or erbium or europium complex, 5- (4'-methacrylamidomethyl) phenyl-10 , 15,20-Triphenyl-21H, 23H-
Porphine and its magnesium or manganese or zinc or iron (III) chloride or yttrium or erbium or europium complex, 4-acryloyloxyphthalocyanine and its magnesium or manganese or iron or copper or zinc complex, 4-methacryloyloxyphthalocyanine and its magnesium or manganese Or iron or copper or zinc complex, 4-acrylamidophthalocyanine and its magnesium or manganese or iron or copper or zinc complex,
4-methacrylamidophthalocyanine and its magnesium or manganese or iron or copper or zinc complex, N-methyl-4-acrylamidophthalocyanine and its magnesium or manganese or iron or copper or zinc complex, N-methyl-4-methacrylamidophthalocyanine and its Magnesium or manganese or iron or copper or zinc complex, 5
-(4'-acryloyloxy) phenyl-21H, 23H
-Porphine and its magnesium or manganese or zinc or iron (III) chloride or yttrium or erbium or europium complex, 5- (4'-methacryloyloxy) phenyl-21H, 23H-porphine and its magnesium or manganese or zinc or iron chloride ( III) or yttrium or erbium or europium complexes, 5
-(4'-Acrylamido) phenyl-21H, 23H-porphine and its magnesium or manganese or zinc or iron (III) chloride or yttrium or erbium or europium complex, 5- (4'-methacrylamido) phenyl-21H, 23H- Porphin and its magnesium or manganese or zinc or iron (III) chloride or yttrium or erbium or europium complex, 5- (4 '
-Acryloyloxy) phenyl-10,15,20-triphenyl-21H, 23H-porphine and its magnesium or manganese or zinc or iron (III) chloride or yttrium or erbium or europium complex, 5- (4'-
Methacryloyloxy) phenyl-10,15,20-triphenyl-21H, 23H-porphine and its magnesium or manganese or zinc or iron (III) chloride or yttrium or erbium or europium complex, 5- (4'-
Acrylamide) phenyl-10,15,20-triphenyl-
21H, 23H-porphine and its magnesium or manganese or zinc or iron (III) chloride or yttrium or erbium or europium complex, 5- (4'-methacrylamido) phenyl-10,15,20-triphenyl-21
H, 23H-porphine and its magnesium or manganese or zinc or iron (III) chloride or yttrium or erbium or europium complex etc. are mentioned.

Next, the surfactant and electron acceptor surrounding the amphipathic polymer electrolyte will be specifically described. First, as the surfactant, for example, the cationic compounds represented by the general formulas (V) to (VI) shown in FIG. 8 are used. In the general formula (V), R ₄ is a C _{8 to} C ₁₈ alkyl group, R ₅ is a C _{1 to} C ₁₈ alkyl group, and X ₂ is C.
1 or Br, and in the general formula (VI), R ₆ is C ₈
To C ₁₈ alkyl group, R ₇ is H or CH ₃ , X ₃ is C
1, Br or I.

Specific surfactants of the general formula (V) include, for example, n-decyltrimethylammonium chloride, n-decyltrimethylammonium bromide,
n-dodecyltrimethylammonium chloride, n-
Dodecyltrimethylammonium bromide, n-hexadecyltrimethylammonium chloride, n-hexadecyltrimethylammonium bromide, n-octadecyltrimethylammonium chloride, n-octadecyltrimethylammonium bromide, di-n-
Dodecyldimethylammonium chloride, di-n-dodecyldimethylammonium bromide and the like can be mentioned.

Specific surfactants of the general formula (VI) include, for example, n-decylpyridinium chloride, n-decylpyridinium bromide, n-dodecylpyridinium chloride, n-dodecylpyridinium bromide, n-dodecylpyridinium. Iodide, n
-Tetradecylpyridinium chloride, n-tetradecylpyridinium bromide, n-hexadecylpyridinium chloride, n-hexadecylpyridinium bromide, n-hexadecylpyridinium iodide,
Examples include n-octadecylpyridinium chloride, n-octadecylpyridinium bromide, n-dodecylpicolinium chloride, n-dodecylpicolinium bromide, n-octadecylpicolinium chloride, n-octadecylpicolinium bromide, n-octadecylpicolinium iodide. Be done.

Next, as an electron acceptor, for example, FIG.
The compounds represented by the general formulas (VII) to (VIII) shown in are used. In the general formula (VII), R ₈ is C ₁ to
C ₃ alkyl group or benzyl group, X ₃ is Cl or Br
Or I or CH ₃ SO ₄ or ρ-toluenesulfonyl,
In the general formula (VIII), R ₉ is a C ₁ -C ₃ alkyl group or a benzyl group, R ₁₀ is a C 2-6 alkylene group or a xylylene group, and X ₄ is Cl, Br or I.

Specific compounds of the general formula (VII) include
For example, N, N'-dimethyl-4,4'-bipyridinium dichloride, N, N'-dimethyl-4,4'-bipyridinium dibromide, N, N'-dimethyl-
4,4′-bipyridinium bis (methylsulfate), N, N′-dimethyl-4,4′-bipyridinium bis (р-toluenesulfonate), N, N′-di (n
-Propyl) -4,4'-bipyridinium dichloride, N, N'-di (n-propyl) -4,4'-bipyridinium dibromide, N, N'-di (n-propyl) -4,4'- Bipyridinium bis (р-toluenesulfonate), N, N'-dibenzyl-4,4'-bipyridinium dichloride, N, N'-dibenzyl-
4,4'-bipyridinium dibromide, N, N'-
Dibenzyl-4,4'-bipyridinium diiodide, N, N'-dibenzyl-4,4'-bipyridinium bis (р-toluenesulfonate), N, N'-diphenyl-4,4'-bipyridinium dichloride,
N, N'-diphenyl-4,4'-bipyridinium dibromide etc. are mentioned. Although not included in the general formula (VII), N, N′-bis (3-sulfonatepropyl)
-4,4'-bipyridinium etc. can also be used.

Alternatively, specific compounds of the general formula (VIII) include, for example, 1,3-bis {N- (N'-methyl-4,4'-bipyridyl)} propane tetrachloride, 1,3- Bis {N- (N'-methyl-4,4'-bipyridyl)} propane tetrabromide, 1,3-bis {N- (N'-benzyl-4,4'-bipyridyl)}
Propane tetrachloride, 1,3-bis {N-
(N'-benzyl-4,4'-bipyridyl)} propane tetrabromide, 1,4-bis {N- (N'-methyl-4,4'-bipyridyl)} butane tetrachloride, 1,4-bis { N- (N'-methyl-4,4'-bipyridyl)} butane tetrabromide, 1,4-bis {N- (N'-benzyl-4,4'-bipyridyl)} butane tetrachloride, 1,4- Bis {N- (N'-
Benzyl-4,4′-bipyridyl)} butane tetrabromide, α, α′-bis {N- (N′-methyl-4,
4'-bipyridyl)}-o-xylene tetrachloride, α, α'-bis {N- (N'-methyl-4,4'-
Bipyridyl)}-o-xylene tetrabromide,
α, α′-bis {N- (N′-benzyl-4,4′-bipyridyl)}-o-xylene tetrachloride, α,
α'-bis {N- (N'-benzyl-4,4'-bipyridyl)}-o-xylene tetrabromide, α, α '
-Bis {N- (N'-methyl-4,4'-bipyridyl)}-m-xylene tetrachloride, α, α'-
Bis {N- (N'-methyl-4,4'-bipyridyl)}
-M-xylene tetrabromide, α, α'-bis {N
-(N'-benzyl-4,4'-bipyridyl)}-m-
Xylene tetrachloride, α, α'-bis {N-
(N'-benzyl-4,4'-bipyridyl)}-m-xylene tetrabromide, α, α'-bis {N-
(N'-methyl-4,4'-bipyridyl)}-p-xylene tetrachloride, α, α'-bis {N- (N '
-Methyl-4,4'-bipyridyl)}-p-xylene
Tetrabromide, α, α′-bis {N- (N′-benzyl-4,4′-bipyridyl)}-p-xylene tetrachloride, α, α′-bis {N- (N′-benzyl-4, 4′-bipyridyl)}-p-xylene tetrabromide and the like.

Finally, as the electron-accepting surfactant, for example, the cationic surfactants represented by the general formulas (IX) to (X) shown in FIG. 10 are used. The general formula (X)
In the formula, R ₁₁ is a C ₈ -C ₁₈ alkyl group, and R ₁₂ is C ₁
To C ₁₈ alkyl group or benzyl group, X ₅ is Cl or B
r and X ₆ are Cl, Br, I or CH ₃ SO ₄ , and in the general formula (X), R ₁₃ is a C _{8 to} C ₁₈ alkyl group,
R ₁₄ is an alkylene group having 2 to 6 carbon atoms or a xylylene group, R ₁₅ is an alkyl group having ₁ to ₁₈ carbon atoms or a benzyl group,
X ₇ , X ₈ , and X ₉ are Cl or Br, and X ₁₀ is Cl, Br,
I or CH ₃ SO ₄ .

Specific surfactants of the general formula (IX) include, for example, Nn-dodecyl-N'-methyl-4,
4'-bipyridinium dichloride, N-n-dodecyl-N'-methyl-4,4'-bipyridinium bromide iodide, N-n-dodecyl-N'-methyl-
4,4'-bipyridinium bromide methylsulfate, Nn-dodecyl-N'-benzyl-4,4'-
Bipyridinium dichloride, Nn-dodecyl-
N'-benzyl-4,4'-bipyridinium dibromide, Nn-dodecyl-N'-benzyl-4,4'-
Bipyridinium chloride bromide, Nn-hexadecyl-N'-methyl-4,4'-bipyridinium
Dichloride, Nn-hexadecyl-N'-methyl-
4,4'-bipyridinium bromide iodide,
N-n-hexadecyl-N'-methyl-4,4'-bipyridinium bromide methylsulfate, N-n-
Hexadecyl-N'-benzyl-4,4'-bipyridinium dichloride, Nn-hexadecyl-N'-benzyl-4,4'-bipyridinium dibromide, N
-N-octadecyl-N'-methyl-4,4'-bipyridinium dichloride, Nn-octadecyl-N '
-Methyl-4,4'-bipyridinium bromide iodide, Nn-octadecyl-N'-methyl-4,
4'-bipyridinium bromide methylsulfate, Nn-octadecyl-N'-benzyl-4,4 '
-Bipyridinium dibromide, N, N'-di-n-
Dodecyl-4,4'-bipyridinium dichloride,
N, N'-di-n-dodecyl-4,4'-bipyridinium dibromide, N, N'-di-n-hexadecyl-
4,4'-bipyridinium dichloride, N, N'-
Examples thereof include di-n-hexadecyl-4,4'-bipyridinium dibromide.

Specific examples of the surfactant of the general formula (X) include 1,3-bis {N- (N'-n-dodecyl-4,4'-bipyridyl)} propane tetrachloride, 1,3-bis {N- (N'-n-dodecyl-
4,4'-bipyridyl)} propane tetrabromide, 1,4-bis {N- (N'-n-dodecyl-4,
4'-bipyridyl)} butane tetrabromide, 1,
6-bis {N- (N'-n-dodecyl-4,4'-bipyridyl)} hexane tetrabromide, 1,3-bis {N- (N'-n-hexadecyl-4,4'-bipyridyl)} Propane tetrabromide, 1,4-bis {N
-(N'-n-hexadecyl-4,4'-bipyridyl)} butane tetrabromide, 1,6-bis {N-
(N'-n-hexadecyl-4,4'-bipyridyl)}
Hexane tetrabromide, α, α'-bis {N-
(N'-n-dodecyl-4,4'-bipyridyl)}-o
-Xylene tetrachloride, α, α'-bis {N-
(N'-n-dodecyl-4,4'-bipyridyl)}-o
-Xylene tetrabromide, α, α'-bis {N-
(N'-n-dodecyl-4,4'-bipyridyl)}-m
-Xylene tetrachloride, α, α'-bis {N-
(N'-n-dodecyl-4,4'-bipyridyl)}-m
-Xylene tetrabromide, α, α'-bis {N-
(N'-n-dodecyl-4,4'-bipyridyl)}-p
-Xylene tetrachloride, α, α'-bis {N-
(N'-n-dodecyl-4,4'-bipyridyl)}-p
-Xylene tetrabromide, α, α'-bis {N-
(N'-n-hexadecyl-4,4'-bipyridyl)}
-O-xylene tetrachloride, α, α'-bis {N- (N'-n-hexadecyl-4,4'-bipyridyl)}-o-xylene tetrabromide, α, α'-
Bis {N- (N'-n-hexadecyl-4,4'-bipyridyl)}-m-xylene tetrachloride, α,
α'-bis {N- (N'-n-hexadecyl-4,4 '
-Bipyridyl)}-m-xylene tetrabromide,
α, α'-bis {N- (N'-n-hexadecyl-4,
4′-bipyridyl)}-p-xylene tetrachloride, α, α′-bis {N- (N′-n-hexadecyl-
4,4'-bipyridyl)}-p-xylene tetrabromide and the like.

As described above, when such a surfactant is added to the aqueous solution of the amphipathic polymer electrolyte, the hydrophilic group of the polymer electrolyte and the hydrophilic group of the surfactant having the opposite electric charge are added. Are ionically bound and precipitate. The precipitate is dried to obtain the ion complex used in the present invention as a powder. In the present invention, a non-polar medium is used as the medium surrounding the ion complex thus obtained.

Specific non-polar media include solvents such as toluene, benzene, xylene, ethylbenzene and other aromatic hydrocarbons. A solid medium (matrix) may be used as the medium. For example, there are polymers obtained by polymerizing monomers such as divinylbenzene, styrene, bromostyrene, methylstyrene, and styrene to which a small amount of MMA is added.

Hereinafter, the present invention will be described in more detail with reference to Reference Examples and Examples, but the present invention is not limited thereto.

[0040]

【Example】

[Reference Example] (1) Synthesis of Pyrene Monomer <First Step> 5.09 g of 1-Pyrenecarboxaldehyde was charged into an autoclave together with 1.5 g of activated Raney Ni, afterwards,
80 ml of distilled dimethylformamide, previously cooled with dry ice-methanol, and 20 ml of liquid ammonia were added little by little to the autoclave.

Next, H ₂ gas was added until the pressure in the autoclave reached 82 kg / cm ³ . Then, heated to 65 to 75 ⁰ C, for 3 hours and reacted under conditions of inner pressure 92~96kg / cm ³ at that temperature. Raney Ni was removed from the reaction product solution by filtration, and the filtrate was concentrated with an evaporator. The residue was extracted 3 times with 500 ml of 1M aqueous hydrochloric acid solution in a boiling water bath. The resulting aqueous hydrochloric acid solution was allowed to cool, and the precipitated hydrochloride was filtered and dried. Yield 2.08 g. (Yield 35.1%) ・¹ H-NMR (DMSO-d6) data (free amine form) 4.4 (s, 2H) 7.9-8.6 (m, 9H) ・ Elemental analysis calculation for C ₁₇ H ₁₄ HCl Value: C: 84.25%; H: 5.72%; N: 4.68% ・ Actual value C: 84.06%; H: 5.72%; N: 4.68% <Second stage> 2.37 g of the hydrochloride obtained in the first stage ( 8.85 x 10
^-3 mol) was placed as it was in a three-necked flask containing benzene, and a small amount of hydroquinone was added. Then, 24.7 cc (1.77 × 10 ^-1 mol) of triethylamine was added, and after stirring for a while, it was diluted with benzene. Then, 10 ml (1.04 × 10 ⁻¹ mol) of methacrylic acid chloride was gradually added dropwise. The mixture was stirred as it was overnight, and triethylamine hydrochloride was removed by suction filtration. The filtrate (benzene layer) was saturated saline four times,
Then, it was washed 5 times with a 1 M aqueous hydrochloric acid solution, and then washed with saturated saline until the washing solution became neutral. In addition, 1 benzene layer
It was washed 5 times with an aqueous solution of sodium hydrogen carbonate M, and then washed with saturated saline until the washing liquid became neutral. Then, the benzene layer was dried with anhydrous magnesium sulfate overnight.

Finally, magnesium sulfate was removed from the benzene layer by filtration, and benzene was evaporated. The obtained solid was recrystallized twice from hexane to give 1.71 g (yield
(64.5%) to obtain a pyrene monomer. The product was pale yellow needle crystals (mp. 145-146.5 ° C).・¹ H-NMR (CDCl ₃ ) data 3.0 (s, 3H), 5.2 (d, 2H), 5.3 (s, 1H), 5.7 (s, 1H), 6.2 (s, 1H), 7.9-8.4 (m , 9H) ・ Elemental analysis calculated for C ₁₇ H ₁₄ NO: C: 84.25%; H: 5.72%; N: 4.60% ・ Actual value C: 84.25%; H: 5.72%; N: 4.68% (2) 1 -Synthesis of adamantyl methacrylamide 1-adamantyl amine 16.2 g (1.07 × 10 ^-1 mol), 30
Charge into a 3-necked flask containing 0 ml of benzene, add 13.1 g (1.29 × 10 ^-1 mol) of triethylamine, stir for a while while cooling in an ice bath, and then add 13.0 g of methacrylic acid chloride (1.25 × 10 ^-1 mol) was gradually added dropwise. The mixture was stirred in the ice bath as it was for 30 minutes and then at room temperature for 12 hours, and then triethylamine hydrochloride was removed by suction filtration.

The filtrate (benzene layer) was washed with saturated saline four times,
Then, it was washed 5 times with a 1 M aqueous hydrochloric acid solution, and then washed with saturated saline until the washing solution became neutral. In addition, 1 benzene layer
It was washed 5 times with an aqueous solution of sodium hydrogen carbonate M, and then washed with saturated saline until the washing liquid became neutral. Then, the benzene layer was dried with anhydrous magnesium sulfate overnight. Then, magnesium sulfate was removed from the benzene layer by filtration, and benzene was evaporated. The obtained solid was recrystallized twice with hexane, and the yield was 10.2 g (yield 43.5%).
Obtained adamantyl methacrylamide. The product was colorless needle crystals (mp. 104-105 ° C).・¹ H-NMR (CDCl ₃ ) data 1.6-2.0 (m, 15H), 2.0 (s, 3H), 5.2 (s, 1H), 5.3 (s, 1H), 5.6 (s, 1H) ・ C ₁₄ H ₂₁ Elemental analysis calculated for NO: C: 76.67%; H: 9.65%; N: 6.39% ・ Actual value C: 76.76%; H: 9.73%; N: 6.46% (3) Synthesis of cyclododecyl methacrylamide Cyclododecyl Amine 25g (1.36 × 10 ^-1 mol) was charged into a 3-necked flask containing 1 liter of benzene, then 18.1 g (1.79 × 10 ^-1 mol) of triethylamine was added, and while cooling in an ice bath, After stirring, 17.4 g (1.66 × 10 ^-1 mol) of methacrylic acid chloride was gradually added dropwise. The mixture was stirred in the ice bath as it was for 30 minutes and then at room temperature for 12 hours, and then triethylamine hydrochloride was removed by suction filtration.

The filtrate (benzene layer) was washed with saturated saline four times,
Then, it was washed 5 times with a 1 M aqueous hydrochloric acid solution, and then washed with saturated saline until the washing solution became neutral. In addition, 1 benzene layer
It was washed 5 times with an aqueous solution of sodium hydrogen carbonate M, and then washed with saturated saline until the washing liquid became neutral. Then, the benzene layer was dried with anhydrous magnesium sulfate overnight. Then, magnesium sulfate was removed from the benzene layer by filtration, and benzene was evaporated. The obtained solid was recrystallized twice with hexane to obtain cyclododecyl methacrylamide with a yield of 18.9 g (yield 55.2%). The product was colorless needles (mp. 157-158 ° C).・¹ H-NMR (CDCl ₃ ) data 1.1-1.8 (m, 23H), 2.0 (s, 3H), 4.1 (s, 1H), 5.3 (s, 1H), 5.6 (s, 1H) ・ C ₁₆ H ₂₉ Calculated elemental analysis for NO: C: 76.31%; H: 11.63%; N: 5.71% ・ Actual value C: 76.31%; H: 11.71%; N: 5.61% (4) Amphiphilic polyelectrolyte (MAPy1Ad50) )) 1 mmol of the pyrene monomer synthesized in (1) above, (2)
50mmo of 1-adamantyl methacrylamide synthesized in
l, 2-acrylamido-2-methylpropanesulfonic acid (AMPS monomer) 49 mmol, and azoisobutyronitrile 0.5 mmol as a polymerization initiator were prepared. These were added in amounts such that the total monomer concentration would be 10 wt%. It was dissolved in dimethylformamide (solvent).

This solution was placed in a polymerization ampoule, degassed 3 times by a rotary pump, and further degassed 2 times by a diffusion pump, and then the ampoule was sealed. This monomer was polymerized by placing this ampoule in a thermostat at 60 ° C. and leaving it for about 10 hours. The product liquid was taken out of the ampoule and then reprecipitated 3 times with ether to obtain a polymer powder.

When this powder was dissolved in water, it was completely dissolved. An aqueous NaOH solution was added to the obtained aqueous solution, and this mixed solution was dialyzed for about 10 days. During this time, the water was changed twice a day. Small molecules were removed by dialysis. After that, concentrate the aqueous solution,
Lyophilized. Thus, an anionic amphiphilic polyelectrolyte (MAPy1Ad50) was obtained. (5) Synthesis of amphiphilic polyelectrolyte (MAPy1Cd50) 1 mmol of pyrene monomer synthesized in the previous section (1), the previous section (3)
50 mmol of cyclododecyl methacrylamide synthesized in
49 mmol of 2-acrylamido-2-methylpropanesulfonic acid (AMPS monomer) and 0.5 mmol of azoisobutyronitrile as a polymerization initiator were prepared, and dimethylformamide was added in such an amount that the total monomer concentration would be 10 wt%. It was dissolved in (solvent).

This solution was placed in a polymerization ampoule, degassed 3 times by a rotary pump, and further degassed 2 times by a diffusion pump, and then the ampoule was sealed. This monomer was polymerized by placing this ampoule in a thermostat at 60 ° C. and leaving it for about 10 hours. The product liquid was taken out of the ampoule and then reprecipitated 3 times with ether to obtain a polymer powder.

When this powder was dissolved in water, it was completely dissolved. An aqueous NaOH solution was added to the obtained aqueous solution, and this mixed solution was dialyzed for about 10 days. During this time, the water was changed twice a day. Small molecules were removed by dialysis. After that, concentrate the aqueous solution,
Lyophilized. Thus, an anionic amphiphilic polyelectrolyte (MAPy1Cd50) was obtained. (6) Synthesis of ion complex (C0 (Py1Ad50BVBr)) Amphiphilic polyelectrolyte (MAPy1Ad50) 0.10 synthesized in (4)
5 g was dissolved in 30 cc of pure water.

On the other hand, 0.234 g of benzyl viologen dibromide which is an electron acceptor was added to 9 cc of pure water and didodecyldimethylammonium bromide (DDAB) which was a surfactant.
0.0462 g was dissolved in 50 cc of pure water. To the former,
The latter two types were added dropwise little by little in the order listed, and the resulting precipitates were collected by a centrifuge, placed in a dialysis membrane and desalted. afterwards,
The aqueous solution was concentrated and freeze dried.

The NMR spectrum of the ion complex (whitish powder) thus obtained is shown in FIG. (7) Synthesis of ion complex (C0 (Py1Cd50BVCl)) Amphiphilic polyelectrolyte (MAPy1Cd50) 0.05 synthesized in (5)
66 g was dissolved in 15 cc of pure water.

On the other hand, 0.192 g of benzyl viologen dichloride as an electron acceptor and 0.0462 g of didodecyldimethylammonium bromide (DDAB) as a surfactant were added to 250 c of
Dissolved in pure water of c. The latter was added dropwise to the former little by little, and the resulting precipitate was collected by a centrifuge, put in a dialysis membrane and desalted. Then, the aqueous solution was concentrated and freeze-dried.

The NMR spectrum of the ion complex (whitish powder) thus obtained is shown in FIG. When the ion complexes (6) and (7) were added to a hydrophobic solvent such as benzene, toluene, acetonitrile, chloroform and ethyl acetate, they rapidly dissolved. On the other hand, the amphipathic polyelectrolytes of (4) and (5) were completely insoluble in these solvents. [Example] The ion complex of (6) was subjected to OD at 355 nm.
It is dissolved in various organic solvents (methanol, acetonitrile, benzene) so that the ratio becomes about 0.5, and the pulse of 355 nm which is the third harmonic of the YAG laser is applied to this solution. Then, electrons move from the donor to the acceptor, and a charge separation state is generated. With laser photolysis,
When monitored by absorption of the cation radical of the electron acceptor benzyl viologen (400 nm), a remarkable difference was observed in the initial Decay curve in benzene, which is a non-polar solvent, and a very slow reverse electron transfer reaction was observed. It was The results are shown in Fig. 13.

[0053]

As described above, according to the mixture of the present invention, it is possible to prolong the life of the ion-complexed charge-separated state by using a non-polar medium. Therefore, the mixture of the present invention, when the amphipathic polyelectrolyte is dispersed or dissolved in a non-polar medium while preserving the microphase-separated structure, and charge-separated between the donor and acceptor by light or the like. Useful,
If the donor-acceptor in the long-life charge separation state is used, it can be considered to be used as an optical functional material (for example, photochromic dye, organic pigment for PHB memory, nonlinear material, etc.).

[Brief description of drawings]

FIG. 1 is a conceptual diagram schematically illustrating the molecular structure of an ion complex of the present invention.

FIG. 2 is a conceptual diagram schematically illustrating the molecular structure of the ion complex of the present invention.

FIG. 3 is a diagram showing an NMR chart.

FIG. 4 is a diagram showing a molecular formula of an amphipathic polyelectrolyte.

FIG. 5 is a diagram showing a molecular formula of a monomer.

FIG. 6 is a diagram showing a molecular formula of a monomer.

FIG. 7 is a diagram showing a molecular formula of a monomer.

FIG. 8 is a diagram showing a molecular formula of a surfactant.

FIG. 9 is a diagram showing a molecular formula of an electron acceptor.

FIG. 10 is a diagram showing a molecular formula of an electron-accepting surfactant.

FIG. 11 is a diagram showing an NMR chart.

FIG. 12 is a diagram showing an NMR chart.

FIG. 13 is a diagram showing Decay curves of viologen cation radicals in various solvents by laser photolysis.

[Explanation of symbols]

1a ₁ Hydrophobic group 1a ₂ Hydrophilic group 1a Amphiphilic polyelectrolyte 1b Surfactant 1c ₁ Electron acceptor 1c ₂ Electron accepting surfactant

Claims (1)

[Claims] 1. A mixture of an ion complex and a medium, wherein the ion complex is a "microphase separation in which a hydrophilic group wraps around an aggregate phase of a hydrophobic group partially containing an electron-donating hydrophobic group. Amphipathic polyelectrolyte having a "structure", and a surfactant and an electron acceptor or an electron accepting surfactant or an electron acceptor and an electron accepting surfactant or a surfactant and an electron bound to the outside of the amphiphilic polyelectrolyte An acceptor and an electron-accepting surfactant, wherein the medium is non-polar.