JP2001335709A - Functional reverse microemulsion and microparticle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a reverse microemulsion containing an amphipathic star polymer in which the central skeleton is a porphyrin exhibiting photocatalytic, function, or the like and at least one metal salt, at least one water-soluble polymer, or at least one pigment and to prepare microparticles comprising a composite material of the amphipathic star polymer with a metal oxide or a metal salt and formed by a chemical reaction in the reverse microemulsion. SOLUTION: Provided are a functional reverse microemulsion prepared by dispersing an aqueous liquid in a hydrophobic oily medium containing its amphipathic star polymer in which arms are made of an amphipathic polymer and the central skeleton is the porphyrin or a metal porphyrin and which is represented by the formula (wherein P is an amphipathic linear polymer bonded to the corresponding benzene ring; M is a hydrogen or a metal atom; and (n) is an integer of 1-3) and the microparticle comprising a composite material of the amphipathic star polymer with the metal oxide or the metal salt and formed by the chemical reaction in the emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an oily medium containing a porphyrin having a photofunction, a catalytic function, and a dye function or an amphiphilic star-shaped polymer having a metalloporphyrin as a central skeleton and dispersed in water or an aqueous solution. The present invention relates to a reverse microemulsion to be used and fine particles comprising a complex of an amphiphilic star polymer and a metal or a metal salt formed by a chemical reaction in the reverse microemulsion.

[0002] The present invention relates to a reversed-phase microemulsion containing potentially polymerizable metal alkoxides in an oily medium of a reverse microemulsion by self-assembly of a star polymer. Further, the present invention relates to an inverse microemulsion containing various water-soluble substances, for example, water-soluble metal salts, a water-soluble polymer, a water-soluble biopolymer, and a water-soluble dye, in water droplets of the inverse microemulsion.

[0003]

2. Description of the Related Art Inverted microemulsions are an industrially important technology that has grown rapidly since the late 1980s, and has been used as a microreactor in various microparticles and microcrystal materials such as inorganic materials, organic-inorganic hybrid materials,
It is widely used for manufacturing semiconductor materials, dye materials and the like.

[0004] Inverted microemulsions and their production techniques are generally based on low molecular neutral surfactants, such as the trade name Tr
ItonX-100: Poly (oxyethylene) tertiary octyl phenyl ether, or an ionic surfactant such as AOT: bis (2-ethylhexyl, sulfosuccinate) or the like is often used.

[0005] Recently, attention has been focused on the production of an inverse microemulsion using a linear amphiphilic block copolymer as a surfactant. In recent years, application of a low molecular surfactant or an inverse microemulsion from an amphiphilic block polymer as a microreactor has been rapidly developed, and is considered to be an important fundamental technology for creating advanced materials.

For example, by synthesizing a conjugated photoconductive polymer, poly (p-phenylenevinylene) from a water-soluble sulfonium monomer in a reversed-phase microemulsion, a product having a significantly increased molecular weight can be obtained. Known "Chemistry of Materials" (Chem.
Mater.) 10, 1065, 1998) ".

[0007] It is also known that by producing an inorganic semiconductor material and a metal catalyst material in an inverse microemulsion, their particle size and surface structure can be controlled on a nanoscale. Chem. Reviw),
87, 877, 1987; Nature
403, 65, 2000 ".

It is also known that an orderly film is produced by immersing the substrate surface in an inverse microemulsion solution containing a metal alkoxide, Langmuir, Vol. 13, p. 4295, 1997.
Year". When the amphiphilic block polymer is used as a surfactant or dispersant of an inverse microemulsion, it has been proposed that a polymer of the dispersant is hybridized to metal fine particles growing in the water droplets, `` Chemistry of Materials ( Chem. Mater.), 7, 1178, 19
95 years. "

However, the production of the inverse microemulsion by the above method is usually carried out by using a conventional low molecular surfactant (A
OT, Triton X-100, etc.) and polymer surfactants (polyethylene oxide-block-polypropylene oxide, polystyrene-block-polymethacrylic acid, etc.). That is, the surfactant had no other function other than the function of dispersing water droplets in oil.

[0010]

An object of the present invention is to provide a porphyrin having a photofunction, a catalytic function and a dye function in its central skeleton and containing various metal salts, water-soluble polymers or dyes. Inverted microemulsion of amphiphilic star-shaped polymer, composite of amphiphilic star-shaped polymer and metal oxide or metal salt formed by chemical reaction in the inverse microemulsion and useful for photocatalyst support and the like An object of the present invention is to provide fine particles composed of a body.

[0011]

Means for Solving the Problems As a result of diligent studies to solve the above-mentioned problems, the present invention has found that an amphiphilic polymer represented by the general formula (I) is used as an arm and porphyrin or metalloporphyrin is used as a central skeleton. An inverse microemulsion in which water droplets are dispersed in an organic phase by dissolving an amphiphilic star polymer having in oil, adding water or an aqueous solution of a water-soluble compound to the solution, and stirring the aqueous / organic mixture. Were found to be easily and stably formed, and the present invention was completed.

That is, the present invention relates to a hydrophobic oil-based polymer comprising an amphiphilic polymer represented by the general formula (I) as an arm and containing an amphiphilic star polymer having porphyrin or metalloporphyrin as a central skeleton. This is a functional inverse microemulsion characterized in that an aqueous liquid is dispersed in a medium. General formula (I)

[0013]

Embedded image

(Wherein P represents a linear polymer having an amphipathic property bonded to a benzene ring, M represents hydrogen or a metal atom, and the metal atom is iron, manganese, zinc, copper, tin, molybdate, Or a transition metal such as ruthenium, or
Represents a metal selected from rare earth metals such as europium and gadolinium, and n represents an integer of 1 to 3. )

The functional inverse microemulsion of the present invention contains a metal alkoxide in a hydrophobic oily medium,
The metal alkoxide is, in particular, one or more compounds selected from the group consisting of alkoxysilane, alkoxytitanium, alkoxyzircon and aluminum alkoxide, and an aqueous liquid containing a water-soluble polymer, wherein the water-soluble polymer is In particular, one or more synthetic polymers selected from the group consisting of polymethacrylic acid, polyacrylic acid, polyacrylamides, and polyoxazolines, or the water-soluble polymer is selected from the group consisting of polypeptides, DNAs, and polysaccharides. Including one or more biopolymers.

According to the present invention, an aqueous liquid contains a water-soluble metal salt, and the metal of the water-soluble metal salt is preferably calcium, barium, iron, manganese, zinc, copper, cadmium, palladium, platinum, molybdenum, ruthenium, or the like. Silver,
Functional inverse microemulsion which is a metal selected from the group consisting of gold, zirconium, cesium, iridium, europium, and gadolinium is included.

The present invention also relates to an aqueous liquid containing an anionic compound or a water-soluble reducing agent compound, wherein the anionic compound is preferably sodium chloride, sodium bromide, sodium iodide, sodium carbonate, phosphorus carbonate or the like. A compound selected from the group consisting of sodium oxalate and sodium sulphide; and the water-soluble reducing compound is at least one compound selected from the group consisting of sodium borohydride, oxalic acid, sodium oxalate and hydrazine. A functional inverse microemulsion or an aqueous liquid containing a water-soluble dye, wherein the water-soluble dye is at least one dye selected from the group consisting of rhodamines, porphyrins, phthalocyanines and stilbazoles Includes reverse microemulsion.

Further, the present invention uses the above-mentioned functional inverse microemulsion as a field of a chemical reaction, and performs a reaction at the interface of the liquid sphere or a chemical reaction inside the sphere, thereby forming a star polymer and a metal compound, Alternatively, the present invention provides fine particles hybridized with a metal cluster, and particularly provides fine particles such as spherical fine particles and hollow spherical fine particles. Among them, formed by a sol-gel reaction of a metal alkoxide, including fine particles composed of a composite of an amphiphilic star polymer and a metal oxide, particularly the metal oxide is silicon oxide, titanium oxide, zircon oxide, aluminum oxide And at least one kind of fine particles selected from the group consisting of:

The present invention also includes fine particles comprising a complex of an amphiphilic star polymer and a metal salt formed by an ion exchange reaction of the metal salt, wherein the metal salt is composed of calcium, barium, iron, or the like. , Manganese, zinc, copper, cadmium, palladium, platinum, molybdenum, ruthenium, silver, gold, zirconium, cesium, iridium, europium, gadolinium, a metal halide selected from the group consisting of metals, sulfurized metals, carbonated metals, It contains fine particles composed of a composite of a star polymer which is a phosphorylated metal and a metal salt.

[0020]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Unlike the conventional concept of a surfactant, a molecule acting as a surfactant has a functional group itself, and a functional inverse microemulsion formed by the functional group is unique to the functional group. Additional functions can be provided. Such an inverse microemulsion is used for the production of a microreactor having a catalytic function, composite fine particles embedded with a functional group, or a multilayer film material (gas sensor, biosensor, optical sensor, memory material, cancer diagnostic agent / therapeutic agent, etc.). New technology for the future.

[0021] Surfactants in conventional methods consist of substances of linear molecular structure, and the inverse microemulsions formed by them are less reliable in their domain structure and their long-term stability. Making a polymer that acts as a surfactant have a branched structure instead of a linear structure
It is considered that the entangled interaction between the branched chains of the amphiphilic polymer having a branching property is useful for improving the stability of the water droplet domain in the inverse microemulsion.

Therefore, the present inventors disperse an aqueous liquid in a hydrophobic oily medium containing an amphiphilic polymer as an arm and an amphiphilic star polymer having porphyrin or metalloporphyrin as a central skeleton. A functional inverse microemulsion was prepared. As a result, since only one porphyrin residue is contained in one macromolecule, it is possible to completely prevent the π-plane association that is often seen with a low-molecular porphyrin.

That is, the porphyrin molecule is isolated in a star-shaped polymer having a hierarchical structure at a molecular level. At the same time, the arm structures around the porphyrin are given controlled amphipathicity, and the arms self-assemble in water and oil (a hydrophobic oily medium). As a result, the porphyrin isolated at the molecular level is taken into a liquid sphere having a spatial axis.

In this process, a regular molecular orientation becomes possible for the formation of the inverse microemulsion by the amphipathic nature of the arms, ie, the sparse / hydrophilic arrangement of the arms. That is, the core porphyrin can be contained in the water of the liquid sphere, or the core porphyrin can be extended to the outer layer of the liquid sphere due to the molecular orientation of the arm opposite thereto.

Thus, by changing the sequence of the amphipathic blocks of the arms, the position of the porphyrin in the resulting liquid sphere can be controlled. As described above, by controlling the position of the porphyrin contained in the microsphere or submicroscale liquid sphere, various functions of the liquid sphere can be highly developed.

The amphiphilic star polymer having porphyrin as the central skeleton used in the present invention is a linear polymer having porphyrin fixed at the center of the star polymer and having an amphiphilic group on the benzene ring in the porphyrin skeleton. It has a molecular structure in which a polymer substituent is substituted, and has a general formula (I)

[0027]

Embedded image

(Wherein P represents a linear polymer having an amphipathic property bonded to a benzene ring, M represents hydrogen or a metal atom, and the metal atom is iron, manganese, zinc, copper, tin, molybtenium, Or a transition metal such as ruthenium, or
Represents a metal selected from rare earth metals such as europium and gadolinium, and n represents an integer of 1 to 3. )
Is represented by

The amphiphilic linear polymer bonded to the benzene ring is, for example, polyoxazoline,
It is a block copolymer or a random copolymer of polystyrene, polyacrylamide and polyacrylates.

A general method for synthesizing a star-shaped polymer having an amphiphilic polymer as an arm and porphyrin as a central skeleton is known, for example, by using a methylphenyl porphyrin halide as a cationic living ring-opening polymerization initiator for oxazoline. It is synthesized according to a conventional cationic polymerization reaction. Or, a halogenated methylphenylporphyrin,
It can be synthesized by using a monomer having a polymerizable unsaturated double bond such as styrene, methacrylate or acrylamide as a living radical polymerization initiator in the presence of copper chloride and bipyridine according to a known and commonly used radical polymerization reaction.

The star polymer represented by the general formula (I) of the present invention having an amphiphilic polymer as an arm and having porphyrin as a central skeleton can be produced, for example, according to the following production method.

The porphyrin derivative having a methyl halide group and the polar solvent are sufficiently stirred to completely dissolve the porphyrin derivative. After adding a 20-fold molar or more 2-oxazoline compound (hereinafter referred to as a first monomer) to the porphyrin derivative to this solution, 40 ° C.
The reaction is carried out while stirring at the above temperature.

After confirming that the first monomer was consumed by 30% or more by gas chromatography or ¹ H-NMR (nuclear magnetic resonance spectrum), 20-fold mol or more of the 2-oxazoline compound (hereinafter referred to as second monomer) ) And continue the reaction with stirring at the same or higher temperature. After the reaction, add an appropriate amount of methanol solvent,
The mixture is concentrated under reduced pressure. The concentrated polymer solution is poured into an ether solvent to reprecipitate the polymer and recover the polymer. By drying the obtained polymer, an amphiphilic star-shaped oxazoline polymer having a porphyrin having a porphyrin color at the center can be obtained in a yield of 80% or more.

Examples of the 2-oxazoline compound used include, for example, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-α-methylvinyl-2-
2-alkyl-2-oxazolines such as oxazoline and 2-propyl-2-oxazoline; 2-phenyl-2
And 2-allyl-2-oxazolines such as -oxazoline and 2- (4-methylphenyl) -2-oxazoline.

Further, it can be used alone in the synthesis of the polymer in the same manner as the 2-oxazoline compound.
Examples of compounds that can be used in combination with -oxazoline compounds include 1,3-oxazine compounds such as 2-methyl-1,3,4-oxazine and 2-phenyl-1,3,4-oxazine And the like.

The porphyrin derivative having a methyl halide group can be obtained by a known method for obtaining a porphyrin derivative, “Journal of Chemical Society.
Faraday Trans. (J. Chem. Soc. Faraday Trans.
) 93, p. 3945 (1997) "or a method analogous thereto. For example,
A small amount of boron trifluoride / diethyl ether is added to a mixture of benzaldehyde having an iodomethyl group and pyrrole in a molar ratio of 1: 1 in a polar solvent such as chloroform, and the mixture is stirred at room temperature for 1 hour.

Next, while stirring these, a small amount of triethylamine and chloranil are added, and the mixture is heated and refluxed for about 1 hour. After completion of the reaction, the solvent is distilled off under reduced pressure and concentrated. An appropriate amount of methylene chloride is added to the concentrate and the mixture is filtered to collect a solid. The solid substance is recrystallized in a mixed solvent of chloroform and methylene chloride, or is separated and purified using silica gel column chromatography using chloroform as a solvent, whereby a porphyrin having an iodomethyl group is obtained in a yield of 35 to 48%. Obtainable.

The first monomer is used in an amount of 20 to 1000 per mole of the porphyrin derivative having a methyl halide group.
It is preferable to add at a ratio in a molar range,
800 mol is more preferable, and the range of 100 to 200 mol is particularly preferable. The input amount of the second monomer can also conform to the above ratio.

In order to obtain a polymer having a high molecular weight, it is sufficient to increase the above molar ratio. However, the first monomer and the second monomer are used for one methyl group in one molecule of the porphyrin derivative. And a maximum of 400 equivalents can be used.

As for the polymerization reaction temperature, it is desirable to set optimum temperature conditions depending on the reaction solvent used. For example, when acetonitrile is used as a solvent, the reaction temperature is 6
The range of 0-80 degreeC is preferable. When phenylacetonitrile is used as the solvent, the reaction temperature is preferably in the range of 80 to 140C. In setting the reaction temperature, it is desirable to also consider the boiling points of the first monomer and the second monomer used.

The polar solvent used in the reaction may be any conventional polar organic solvent, such as acetonitrile, cyanobenzene, phenylacetonitrile, dimethylamide, and dimethylacetamide. Among them, phenylacetonitrile, Dimethylacetamide is particularly preferred.

Further, the star polymer represented by the general formula (I) of the present invention having an amphiphilic polymer as an arm and having porphyrin as a central skeleton can be produced, for example, according to the following production method.

A porphyrin derivative having an iodomethyl group or a chloromethyl group and a polar solvent are added, and the mixture is sufficiently stirred to completely dissolve the porphyrin derivative. To this solution, 5 times by mole of copper chloride, 8 times by mole of bipyridine, and 20 times or more by mole of a compound having a polymerizable unsaturated double bond (hereinafter, referred to as a first monomer) are added to the porphyrin derivative, Continue the reaction at a temperature above ℃.

After confirming that 50% or more of the first monomer has been consumed by gas chromatography or 1H-NMR, the olefinic compound (hereinafter referred to as “second compound”) has a molar concentration of 20 times or more.
It is called a monomer. ) And continue the reaction with stirring at the same or higher temperature. After completion of the reaction, an appropriate amount of a methanol solvent is added, and the mixture is concentrated under reduced pressure. The concentrated polymer solution is dissolved in methanol or chloroform, and the solution is poured into an ether solvent to recover the polymer by reprecipitating the polymer.

Further, the recovered polymer is dissolved in dimethylformamide, and the solution is permeated into a dimethylformamide solvent through a permeable membrane capable of removing low molecules having a molecular weight of 1,000 or less. After concentrating the remaining polymer solution, the obtained polymer is dried to obtain a porphyrin-centered amphiphilic star olefin polymer having a porphyrin color in a yield of 80% or more.

Examples of the olefin compounds (compounds having a polymerizable unsaturated double bond) include, for example, styrene, methyl methacrylate, tert-butyl methacrylate, tert-butyl acrylate, benzyl methacrylate, hydroxyethyl methacrylate, N, N- Dimethylaminoethyl methacrylate, acrylamide, N,
N-dimethylacrylamide, N-isopropylacrylamide and the like can be mentioned.

For example, when styrene is used as a monomer, the polymerization temperature is preferably in the range of 90 to 130 ° C. When methacrylates and acrylamides are used as monomers, the reaction temperature is 70 to 140.
C. is desirable. To set the reaction temperature, the first
It is desirable to consider the reactivity of the monomer and the second monomer together.

The polar solvent used in this reaction may be any commonly used polar organic solvent. For example, polar solvents such as toluene, anisole, dimethylformamide and dimethylacetamide are preferred.

P consisting of a star-shaped amphiphilic polymer having an amphipathic polymer represented by the general formula (I) and having porphyrin as a central skeleton is represented by P and a monomer X constituting a hydrophilic portion. It is a copolymer with the monomer Y constituting the moiety. The polymer consisting of X and Y is
Although it may be a random polymer, it is preferably a block polymer.

Further, n of the star polymer having an amphiphilic polymer as an arm and having porphyrin as a central skeleton represented by the general formula (I) represents the number of bonds of the polymer P bonded to the benzene ring of the porphyrin skeleton. The number n of bonds represents an integer of 1 to 3, and is preferably 1 or 2. The bonding position of the polymer P bonded to the benzene ring of the porphyrin skeleton may be at the para, meta, or ortho position of the benzene ring with respect to the porphyrin skeleton, but the para position and the ortho position are preferable.

The monomer X constituting the hydrophilic portion may be an oxazoline such as methyl oxazoline or ethyl oxazoline, or methacrylic acid, acrylic acid, acrylamide, N, N-dimethylacrylamide and the like. Examples of the monomer Y constituting the hydrophobic portion include phenyloxazoline, styrene, methyl methacrylate, and benzyl methacrylate.

The polymer P composed of a linear polymer having amphipathic properties is preferably a polymer having a polyoxazoline skeleton. Among them, a polymer P having a polyphenyloxazoline-polymethyloxazoline-block copolymer skeleton and polyphenyloxazoline Those having a polyethyloxazoline-block copolymer skeleton are particularly preferred. Further, those having a polyacrylamide skeleton are also preferable, and among them, polymers, copolymers and block copolymers having an N-Iso-propylacrylamide skeleton are particularly preferable.

The degree of polymerization and the composition of the linear polymer P having amphipathic properties have an important effect in forming an inverse microemulsion.
The range of 0 to 500 is preferable, the range of 50 to 300 is particularly preferable, and the range of 100 to 200 is more preferable. 1
The ratio of the hydrophobic monomer in one polymer P is (hydrophobic monomer) / [(hydrophobic monomer) + (hydrophilic monomer)]
It is preferably within 90 to 10 mol%, particularly preferably within 70 to 40 mol%.

The porphyrin serving as the central skeleton is a complex in which one metal is coordinated in one molecule even if it is a metal-free substance. It may be a metalloporphyrin. As the metal constituting the complex, a transition metal such as iron, manganese, zinc, copper, tin, molybthenium, ruthenium, or europium,
Rare earth metals such as gadolinium are preferred.

Although these star polymers are soluble in a hydrophobic organic solvent, an inverse microemulsion can be prepared by adding an aqueous solution to a hydrophobic solution of the star polymer. Examples of the organic solvent that can be preferably used as the hydrophobic liquid include hexane, cyclohexane, toluene, ethyl acetate, butanol, chloroform, methylene chloride, chlorobenzene, and anisole.

The size of the inverse microemulsion water droplet is
It is related to the weight ratio of water to star polymer (weight of water / weight of polymer), and the weight ratio is preferably 1 to 40,
0 is more preferred. The spherical stability of the liquid sphere of the inverse microemulsion is related to the concentration of the star polymer contained in the hydrophobic organic solvent. For 100 parts by weight of the organic solvent, 0.1 to 4 parts by weight of the star polymer is used. Is preferable.

The alkoxysilane used in the present invention is a silane represented by the general formula R _n Si (OR ′) _4-n .
In the formula, R represents an alkyl group, an aryl group, or a derivative thereof from an organic group. In addition, R ′ has 1 to 1 carbon atoms.
4 represents an alkyl group. Further, n represents an integer of 0 to 2.

Specific examples of these alkoxysilanes include tetramethoxysilane, tetraethoxysilane,
Tetrapropoxysilane, tetrabutoxysilane, tetra-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxylan, ethyltriethoxysilane, n-propyltrimethoxylan, n-propyltriethoxysilane, iso-propyltri Methoxysilane, iso-propyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, vinyltrimethoxysilane,

Vinyltriethoxysilane, 3-glycitoxypropyltrimethoxysilane, 3-glycitoxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-mercaptopropyltomethoxysilane, 3-mercaptotriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane,

3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-chloromethylphenyltrimethoxysilane, p-chloromethylphenyltriethoxysilane, dimethyl Dimethoxysilane, dimethyldiethoxysilane,
Examples include diethyldimethoxysilane and diethyldiethoxycyan. These alkoxysilanes can be used alone or in combination of two or more.

Further, these alkoxysilanes can be used in combination with other metal alkoxides such as alkoxytitanium, alkoxyzircon, and aluminum alkoxide. Examples of metal oxides other than alkoxysilanes used in the present invention include alkoxytitanium, alkoxyzircon, and aluminum oxide.

Examples of the alkoxytitanium include tetramethoxytitanium, tetraethoxytitanium, tetra-propoxytitanium, tetra-iso-propoxytitanium, tetra-n-butoxytitanium, tetra-tert-butoxytitanium and the like. As alkoxy zircon,
For example, tetramethoxy zircon, tetraethoxy zircon, tetrapropoxy zircon, tetra-iso-propoxy zircon, tetra-n-butoxy zircon, tetra-tert-butoxy zircon and the like can be mentioned.

Examples of the aluminum alkoxyside include trimethoxyaluminum, triethoxyaluminum, triplepoxyaluminum, tri-iso-propoxyaluminum, tributoxyaluminum, tri-tert-butoxyaluminum and the like.

The metal alkoxide is preferably added to the oily medium or the inverse microemulsion solution in the form of a bulk or a mixed solution. The amount of metal alkoxide added is preferably 500 parts by weight or more, more preferably 300 parts by weight or more, and particularly preferably at least 300 parts by weight, based on 100 parts by weight of the star polymer. It is.

The water-soluble polymer used in the present invention includes
Examples thereof include poly (methacrylic acid), poly (acrylic acid), poly (acrylamide), poly (methyloxazoline), and poly (vinylpyridine hydrochloride). Further, the water-soluble biopolymer used in the present invention includes poly (glutamic acid), poly (aspartic acid), poly (lysine), cytochrome C, various commercially available DNA powders or aqueous solutions,
Cyclodextrin (α, β and γ forms) and the like.

The concentration of these water-soluble polymers was 10
The polymer is preferably 40 parts by weight or less, more preferably 20 parts by weight or less, based on 0 parts by weight. Water droplets obtained by the above-mentioned inverse microemulsion have a particle size ranging from 200 to 3000 nm depending on the structure and properties of the star polymer.

The metal salts used in the present invention include calcium, barium, iron, manganese, zinc, copper, cadmium, palladium, platinum, molybdenum, ruthenium, silver, gold, zirconium, cesium, iridium, europium, and gadolinium nitrate. Perchlorates or chlorides soluble in water are mentioned. These metal salts can be used alone or in combination with other metal salts. The concentration of these metal salts in water is preferably 2M or less as a molar concentration.

The anionic water-soluble compounds used in the present invention include sodium chloride, sodium bromide, sodium iodide, sodium carbonate, sodium phosphate, sodium sulfide and the like. The water-soluble reducing agent compound is sodium borohydride. Oxalic acid, sodium oxalate, hydrazine and the like. The concentration of these anionic or reducing agent compounds in water is preferably 2 M or less as a molar concentration.

The water-soluble dyes used in the present invention include rhodamine A, rhodamine B, rhodamine WT, tetra (p-methylpyridinimil) porphyrin, tetra (p-sulfonatephenyl) porphyrin, and 4- (dimethylamino) —N-methylstilbazolium tosylate and the like. The concentration of these dyes in water is preferably 0.01 M or less as a molar concentration.

In the above-mentioned inverse microemulsion, a chemical reaction at the liquid-liquid interface between the compound contained in the water of the liquid sphere and the compound contained in the bulk hydrophobic oil phase, for example, a sol-gel reaction of a metal alkoxide, or By the ion exchange reaction of the metal salt, solid fine particles in which the star polymer and the metal oxide or metal salt are hybridized can be produced.

The metal alkoxide used for the sol-gel reaction is preferably an alkoxysilane, an alkoxytitanium, an alkoxyzircon or an alkoxyalumina which is soluble in an oil phase, and particularly preferably an alkoxysilane and an alkoxytitanium. In order to control the sol-gel reaction, the aqueous solution in the liquid sphere is preferably acidic or alkaline, and their pH is 1 or less, or 14 or less.
It is particularly preferable that the above is satisfied.

In causing the sol-gel reaction, the compounds contained in the liquid spheres, due to their solubility in water, do not seep out of the liquid spheres into the hydrophobic oil phase, forming solid particles and simultaneously sealing them inside. Can be
Therefore, it is possible to form a hybrid material having a multi-element structure into one particle.

When the above-mentioned inverse microemulsion is used, when the compound contained in the water of the liquid sphere is mixed with the liquid sphere containing another compound capable of reacting therewith, the compound is subjected to fusion of the emulsions and the like. A solid in which a polymer and a solid inorganic salt are hybridized by a chemical reaction of a compound in a liquid sphere, for example, a precipitation reaction by an ion exchange reaction between silver ions and halogen ions, a precipitation reaction between cadmium ions and sulfur ions, and the like. Fine particles can be produced.

For the production of such polymer / inorganic salt hybrid fine particles, an emulsion containing a metal cation and an emulsion containing an anion are mixed in equal volumes.
It is desirable to react at room temperature. The concentration of the metal cation or anion contained in the liquid sphere is preferably 2M or less, particularly preferably 0.5M or less.

The reverse microemulsion of the present invention is a micro or sub-micro sphere containing porphyrin or metalloporphyrin, which is used in P-450 oxidation catalyst involving porphyrins, photocatalyst in photosynthesis, and photochemical hole burning (PHB). Optical recording materials,
Optical amplification of laser organic dyes, photoelectric conversion elements in the field of optical and electronic devices, solar cells, gas sensors for oxygen and nitrous oxide, DNA quantification sensors in genes and clinics, and photodynamic cancer diagnosis and cancer treatment in a wide range of fields. Useful for the manufacture of composite advanced materials.

Further, the present invention provides an amphiphilic star polymer formed by a sol-gel reaction of a metal alkoxide or an ion exchange reaction of a metal salt in a functional inverse microemulsion in addition to the functions involving porphyrins. Fine particles comprising a composite with a metal oxide or a metal salt are provided. These fine particles are composed of silica, titania, zirconia, and alumina, which are involved in photoactivity, semiconductors, catalysts, catalyst supports, anticorrosive materials, and rare earth metals. It is also usefully used for the production of oxide particles.

[0077]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the scope of these examples. In the following examples, “parts” means “parts by weight” unless otherwise specified.

[0078]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following examples, “parts” means “parts by weight” unless otherwise specified.

[Molecular weight measurement method] High performance liquid chromatography (GPC, manufactured by Tosoh Corporation, HLC-8000, RI detector, TSKgel2000x1 + 3000Hx1 + 5000Hx1 + guardcolumnHx1
-H, solvent DMF, flow rate 1.0 ml / min, temperature 40 ° C).

[Measurement Method of Particle Size and Particle Size Distribution] The micelle particle size and particle size distribution by the dynamic light scattering (DLS) method were measured by Microt.
rac particle size analyzer (Nikkiso Co., Ltd., 9203-UP
A, laser light 780 nm, reflection angle 180 ^° , temperature 25
° C).

(Synthesis Example 1) In the general formula (I), P is a linear polymer having amphiphilicity consisting of poly (methyloxazoline) -poly (phenyloxazoline),
Example of synthesis of star-shaped poly (methyloxazoline-b-phenyloxazoline) (abbreviation: S-MO-b-PO) in which the bonding position and the number of bonds are in four para positions

1-1. [Synthesis example of tetra (p-iodomethylphenyl) porphyrin (abbreviation: TIMPP)] 0.98 g of p-iodomethylbenzaldehyde, pyrrole were placed in a 1000 ml eggplant-shaped flask equipped with a reflux condenser, a three-way cock and a gas bubbling tube. 0.28 g and 400 ml of chloroform were added. This mixed solution was bubbled with argon gas for 10 minutes while stirring with a stirrer. Thereafter, a diethyl ether solution of 0.02 ml of boron tribromide was added, and the mixed solution was stirred at room temperature for 1 hour.

Subsequently, 0.23 ml of triethylamine and 0.74 g of chloranil were added, and the mixture was refluxed for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, the solvent was distilled off under reduced pressure, and the reaction product was concentrated. An appropriate amount of methylene chloride was added to the concentrated solution, followed by filtration to recover an insoluble solid. The solid was dissolved in a small amount of chloroform, separated and purified using a silica column, and tetra (p-iodomethylphenyl) porphyrin 0 was purified. .55 g were obtained.
(Yield 47%) The structure of TIMPP was identified by ¹ H-NMR (nuclear magnetic resonance spectrum), UV-Vis (ultraviolet-visible absorption spectrum), Mass (mass) analysis, and elemental analysis.

¹ H-NMR (300 MHz, CDCl
₃ , in (CH ₃ ) ₄ Si internal standard): δ (ppm): −
2.8 (s, 2H), 4.7 (s, 8H), 7.7-
7.8 (d, 8H), 8.1 to 8.2 (d, 8H),
8.8 (s, 8H)

UV-Vis (in CHCl ₃ ): λmax
(Nm): 419.2, 515.3, 541.5, 59
0.3, 648.8 FAB-Mass: m / z: 1174, 1175

Elemental analysis: (measured value) C = 49.02%,
H = 2.74%, N = 4.65%, (calculated value) C = 4
9.09%, H = 2.92%, N = 4.77%

1-2. [Synthesis of star-shaped poly (methyl oxazoline-b-phenyloxazoline) (abbreviation: S-MO-b-PO) using TIMPP as an initiator] The inside of a 50 ml capacity two-necked flask equipped with a three-way cock was filled with argon gas. After substitution with TIMPP0.
0352 g and 8.0 ml of phenylacetonitrile were added, and the mixture was stirred at room temperature to completely dissolve TIMPP.
To this solution, 1.06 ml of 2-methyl-2-oxazoline corresponding to 400 times the molar number of TIMPP (1.
After the addition of 02g) via a syringe, the mixture was reacted at 100 ° C with stirring for 24 hours.

At this point, the conversion of 2-methyl-2-oxazoline was 98%. After the temperature of the reaction solution was lowered to 60 ° C., 0.883 g of 2-phenyl-2-oxazoline and 4.0 ml of phenylacetonitrile corresponding to 200 times the molar number of TIMPP were added, and then 1 ml of TIMPP was added.
The reaction was carried out with stirring at 00 ° C. for 24 hours. After lowering the temperature of the reaction mixture to room temperature and adding 10 ml of methanol,
The reaction mixture was concentrated under reduced pressure.

The residue was dissolved in 15 ml of methanol,
Pour this solution into 100 ml of tetrahydrofuran,
The polymer was precipitated. The polymer was reprecipitated by the same method, and after suction filtration, the obtained polymer was put into a desiccator in which P2O5 was placed, and dried by suction with an aspirator for 1 hour. Further, the pressure was reduced by a vacuum pump, and the film was dried under vacuum for 24 hours, and star-shaped poly (methyloxazoline-b-phenyloxazoline) (abbreviation: S-MO-b-PO) 1.88
g was obtained. (Yield 96.9%)

The S-MO-b-PO thus obtained had a number average molecular weight of 26,000 as measured by GPC (gel permeation chromatography) and a molecular weight distribution of 1.
47. Further, when the integral ratio between the ethylene proton in the polymer arm and the pyrrol ring proton of porphyrin at the polymer center was calculated by ¹ H-NMR, the average degree of polymerization of each arm was 142. In addition, ¹
The molar composition ratio between the methyl oxazoline residue and the phenyl oxazoline residue measured by H-NMR was 68/32.

<Synthesis Example 2> (In the general formula (I) using TIMPP as an initiator, R is a poly (ethyl oxazoline) -poly (methyl oxazoline) block copolymer having an amphipathic property, which is a block copolymer. Star-shaped poly (ethyl oxazoline-b-methyl oxazoline) which is a polymer and has four substitution positions and the number of substitutions at para position (abbreviation: SE
Synthesis of Ob-MO) After replacing the inside of a 50 ml two-necked flask equipped with a three-way cock with argon gas, the TIMPPP.
0352 g and 8.0 ml of phenylacetonitrile were added, and the mixture was stirred at room temperature to completely dissolve TIMPP.
To this solution, 1.78 g of 2-ethyl-2-oxazoline corresponding to 600 times the molar number of TIMPP was added by a syringe, and the mixture was reacted with stirring at 100 ° C. for 24 hours.

At this point, the conversion of 2-methyl-2-oxazoline was 98%. After lowering the temperature of the reaction solution to 60 ° C., 0.766 g of 2-methyl-2-oxazoline and 4.0 ml of phenylacetonitrile, which are equivalent to 300 times the molar number of TIMPP, were added, and then 10 ml of TIMPP was added again.
The reaction was carried out with stirring at 0 ° C. for 24 hours. The temperature of the reaction mixture was lowered to room temperature, 10 ml of methanol was added, and the reaction mixture was concentrated under reduced pressure.

The residue was dissolved in 15 ml of methanol,
Pour this solution into 100 ml of tetrahydrofuran,
The polymer was precipitated. In the same manner, the polymer was reprecipitated, and after suction filtration, the obtained polymer was placed in a desiccator over phosphorus pentoxide, and suction-dried with an aspirator for 1 hour. Further, the pressure was reduced by a vacuum pump, and the resultant was dried under vacuum for 24 hours, and 2.34 star poly (ethyloxazoline-b-methyloxazoline) (abbreviation: S-EO-b-MO) 2.34
g was obtained. (Yield 91%)

The number average molecular weight of the thus obtained S-EO-b-MO measured by GPC was 25,200.
The molecular weight distribution was 1.45. In addition, when the integral ratio between the ethylene proton in the polymer arm and the pyrrol ring proton of porphyrin in the center of the polymer was calculated by ¹ H-NMR, the average degree of polymerization of each arm was 210. Further, the molar composition ratio of methyl oxazoline residues to ethyl oxazoline residues by ¹ H-NMR measurement was 37.
/ 63.

<Synthesis Example 3> (A linear polymer having an amphipathic property in which, in the general formula (I), R is a poly (methyloxazoline) -poly (ethyloxazoline) copolymer using TIMPP as an initiator. Wherein the substitution position and the number of substitutions are at the para-position of four positions, star-shaped poly (methyloxazoline-co-phenyloxazoline) (abbreviation: S-MO-
Synthesis of (co-PO)) After replacing the inside of a 50 ml two-necked flask equipped with a three-way cock with argon gas, the previously obtained TIMPPP.
0352 g and 8.0 ml of phenylacetonitrile were added, and the mixture was stirred at room temperature to completely dissolve TIMPP.

To this solution was added 2-methyl-2-oxazoline 1.0 equivalent to 400 times the molar number of TIMPP.
After adding 21 g, 1.325 g of 2-phenyl-2-oxazoline corresponding to 300 mol with a syringe, the mixture was reacted with stirring at 60 ° C. for 24 hours.
C. and continued stirring for another 24 hours.

After the temperature of the reaction mixture was lowered to room temperature and 10 ml of methanol was added, the reaction mixture was concentrated under reduced pressure. The residue was dissolved in 15 ml of methanol and the solution was poured into 100 ml of tetrahydrofuran to precipitate the polymer. In the same manner, reprecipitate the polymer, and after suction filtration,
The obtained polymer is placed in a desiccator on which P2O5 is placed, and
Suction dried with aspirator for hours. The pressure was further reduced by a vacuum pump, and the product was dried under vacuum for 24 hours to obtain 2.06 g of star-shaped poly (methyloxazoline-co-phenyloxazoline) (abbreviation: S-MO-co-PO). (88% yield)

The thus obtained S-MO-co-PO
Has a number average molecular weight of 21,000 measured by GPC.
And the molecular weight distribution was 1.32. Also, ¹ H-NM
The integral ratio between the ethylene proton in the polymer arm and the porphyrin ring proton of the porphyrin at the polymer center was calculated from R, and the average degree of polymerization of each arm was 12
It was 4. Further, the molar composition ratio of methyl oxazoline residue to phenyl oxazoline residue measured by ¹ H-NMR was 68/32.

<Synthesis Example 4> (In the general formula (I), R
Is a linear polymer having amphipathic properties comprising a poly (styrene) -poly (acrylamide) block copolymer, in which the substitution position and the number of substitution are para-positions at four positions, star-shaped poly (styrene-b-acrylamide) (Abbreviation: S-St
-B-AAm) 4-1. [Synthesis of Tetra (p-chloromethylphenyl) porphyrin (abbreviation: TCMPP)] In a 1000 ml eggplant type flask equipped with a reflux condenser, a three-way cock and a gas bubbling tube, 0.62 g of chloromethylbenzaldehyde and 0.28 g of pyrrole And 400 ml of chloroform. This mixed solution was bubbled with argon gas for 10 minutes while stirring with a stirrer. Thereafter, a diethyl ether solution of 0.02 ml of boron tribromide was added, and the mixed solution was stirred at room temperature for 1 hour.

Subsequently, 0.23 ml of triethylamine and 0.74 g of chloranil were added, and the mixture was refluxed for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, the solvent was distilled off under reduced pressure, and the reaction product was concentrated. An appropriate amount of methylene chloride was added to the concentrated solution, and the mixture was filtered to collect an insoluble solid.
Separation and purification were carried out using a silica column, and the eluate was evaporated to dryness using a rotary evaporator to obtain tetra (p-
Chloromethylphenyl) porphyrin (abbreviation: TCMP)
P) 0.35 g was obtained. (Yield 45%)

4-2. [Star-shaped poly (styrene-b-acrylamide) using TCMPP as an initiator (abbreviation: S-
Synthesis of St-b-AAm)] The inside of a 50 ml two-necked flask equipped with a three-way cock was replaced with argon gas, and then the previously obtained TCMPP was used.
0.026 g, 0.027 g of copper chloride, 0.084 g of 2,2'-bipyridine, and 2.0 ml of deaerated dimethylformamide bubbled with argon gas were added, and the mixture was stirred at room temperature to completely dissolve the solid. To this solution, add TCM
0.375 g of deaerated styrene corresponding to 120 times the number of moles of PP was added with a syringe, and then 24 hours at 130 ° C.
After reacting with stirring for a time, the reaction temperature was lowered to 60 ° C., and a solution in which 0.426 g of acrylamide was dissolved in 5.0 ml of dimethylamide was added with a syringe while flowing argon gas.

The reaction solution was heated again to 130 ° C.
Stir for 4 hours. The temperature of the reaction mixture was lowered to room temperature, 10 ml of methanol was added, and the reaction mixture was concentrated under reduced pressure. The residue was dissolved in 15 ml of dimethylformamide and the solution was poured into 100 ml of diethyl ether to precipitate the polymer.

The obtained polymer was dissolved again in 10 ml of dimethylformamide, and the solution was permeated into a dimethylformamide solvent for 24 hours through a permeable membrane capable of removing low-molecular weight compounds having a molecular weight of 1,000 or less. The residual liquid is concentrated and reprecipitated,
After suction filtration, the obtained polymer was put into a desiccator on which phosphorus pentoxide was placed, and suction-dried with an aspirator for 1 hour. Further, the pressure was reduced by a vacuum pump, and the resultant was dried under vacuum for 24 hours. Star-shaped poly (styrene-b-acrylamide) in which copper was coordinated with porphyrin (abbreviation: S-St-b-AA)
m) 0.735 g was obtained. (88.9% yield)

The S-St-b-AAm thus obtained
The number average molecular weight measured using GPC was 16,000.
And the molecular weight distribution was 1.25. Also, ¹ H-NM
The integral ratio between the total value of the phenyl proton and the amide proton in the polymer arm and the pyrrol ring proton of the porphyrin at the center of the polymer was calculated from R, and the average degree of polymerization of each arm was 75. Further, ¹ H-NM
The molar composition ratio of the styrene residue to the acrylamide residue determined by R measurement was 34/66.

<Example 1> (Preparation of inverse microemulsion using star-shaped polyoxazoline copolymer) Star-shaped poly (methyloxazoline-phenyloxazoline) (S-MO) obtained in Synthesis Example 3 was added to 80 parts of chloroform. −
(co-PO) 1.5 parts of a star polymer in chloroform solution was prepared. To this solution, 10 parts of water was added, followed by stirring for 5 minutes to obtain a coffee-colored opaque inverse microemulsion liquid. The particle diameter of water droplets in the inverse microemulsion was measured by dynamic light scattering and found to be in the range of 0.03 to 2 μm.

<Example 2> (Preparation of inverse microemulsion using star-shaped polyoxazoline block copolymer) In 80 parts of chloroform, the star-shaped poly (ethyloxazoline-b-methyloxazoline) obtained in Synthesis Example 2 was used. S-EO
−b-MO) was dissolved in 1.5 parts to prepare a chloroform solution of the star polymer. 10 parts of water was added to this solution, and the mixture was stirred for 5 minutes to obtain a coffee-colored translucent inverted microemulsion. When the particle size of water droplets in the inverse microemulsion liquid was measured by the dynamic light scattering method,
It was in the range of 0.03 to 2 μm.

In Example 2, a star-shaped polyoxazoline block copolymer before and after formation of a reverse microemulsion was prepared by ¹ H-NMR method for a reverse microemulsion obtained in a system using heavy chloroform instead of chloroform. By observing the waveform of the proton signal of the linear polymer portion having an amphiphilic group, the copolymer dissolved in deuterated chloroform before adding water was added with water to form an inverse microemulsion. The repeating unit derived from polymethyloxazoline dissolves in the water droplets of the inverse microemulsion, and conversely, the repeating unit derived from polyethyloxazoline
It could be confirmed that it was dissolved in heavy chloroform.

<Example 3> (Preparation of an inverse microemulsion containing tetraethoxysilane in an organic phase and silver nitrate in water droplets) Star-shaped poly (methyloxazoline-phenyloxazoline) obtained in Synthesis Example 3 in 80 parts of chloroform (S-MO-
(co-PO) 1.5 parts was dissolved to prepare a chloroform solution of the star polymer. After dissolving 10 parts of tetraethoxysilane in this solution, a 0.02 M silver nitrate aqueous solution 12
Was added and stirred for 5 minutes to obtain a coffee-colored translucent inverted microemulsion liquid.

<Example 4> (Preparation of an inverse microemulsion containing tetraethoxysilane in an organic phase and polymethacrylic acid in water droplets) The star-shaped poly (methyloxazoline-phenyl) obtained in Synthesis Example 3 was added to 80 parts of chloroform. Oxazoline) (S-MO-
(co-PO) 1.5 parts was dissolved to prepare a chloroform solution of the star polymer. After dissolving 10 parts of tetraethoxysilane in this solution, an aqueous solution containing 1 part of poly (methacrylic acid) is added to 10 parts of water, and the mixture is stirred for 5 minutes.
A coffee-colored translucent inverted microemulsion was obtained.

Example 5 Preparation of Reverse Microemulsion Using (Star-Shaped Polystyrene-Polyacrylamide) Block Copolymer Star-shaped poly (styrene-b-acrylamide) obtained in Synthesis Example 4 was added to 100 parts of toluene. (S-St-b-AAm) 2
The parts were dissolved to prepare a toluene solution of the star polymer.
To this solution, 10 parts of water was added and stirred for 5 minutes to obtain a coffee-colored translucent inverted microemulsion liquid.

Example 6 Preparation of Inverted Microemulsion Containing Tetraethoxysilane in Organic Phase and DNA in Water Droplets In 80 parts of chloroform, the star-shaped poly (methyloxazoline-phenyloxazoline) obtained in Synthesis Example 3 was added. (S-MO-
1.5 parts of (co-EO) were dissolved to prepare a chloroform solution of the star polymer. After dissolving 10 parts of tetraethoxysilane in this solution, an aqueous solution containing 1 part of DNA was added to 10 parts of water, and stirred for 5 minutes to obtain a coffee-colored translucent inverse microemulsion liquid.

<Example 7> (Preparation of inverse microemulsion containing tetraethoxysilane in the organic phase and sodium borohydride in the water droplets) The star-shaped poly (methyloxazoline) obtained in Synthesis Example 3 was added to 80 parts of chloroform. Phenyloxazoline) (S-MO-
1.5 parts of (co-EO) were dissolved to prepare a chloroform solution of the star polymer. After dissolving 10 parts of tetraethoxysilane in this solution, 10 parts of a 5% aqueous sodium borohydride solution was added and stirred for 5 minutes to obtain a coffee-colored translucent inverse microemulsion liquid.

<Example 8> (Synthesis of star polymer / silica / polymethacrylic acid ternary composite spherical fine particles from an inverse microemulsion containing tetraethoxysilane in the organic phase and polymethacrylic acid in the water droplets) 80 parts of chloroform First, the star-shaped poly (methyloxazoline-phenyloxazoline) obtained in Synthesis Example 3 (S-MO-
(co-PO) 1.5 parts was dissolved to prepare a chloroform solution of the star polymer. After dissolving 10 parts of tetraethoxysilane in this solution, 5 parts of a polymethacrylic acid aqueous solution having a concentration of 0.07 g / cm ³ was added, and the mixture was stirred for 5 minutes.
A coffee-colored translucent inverted microemulsion was obtained.

While stirring the inverse microemulsion liquid, 3 parts of a 1M aqueous HCl solution was added to make the inverse emulsion emulsion strongly acidic. This inverse microemulsion was allowed to stand at room temperature for 24 hours to allow the sol-gel reaction of tetraethoxysilane to proceed. The insoluble particles generated in the reaction system are repeatedly washed with ethyl acetate, then replaced with methanol, and repeatedly washed with a centrifugal separator to remove the light purple star-shaped polymer / silica / polymethacrylic acid ternary composite spherical fine particles. Obtained. These spherical fine particles emitted strong red fluorescence under visible light irradiation of a fluorescence microscope. As a result of observation with a transmission electron microscope, the diameter of the spherical particles was 50 to 250 nm. FIG. 1 shows a transmission electron micrograph.

Example 9 Synthesis of Star-Shaped Polymer / Silica Hybrid Hollow Spherical Fine Particles from Reverse Microemulsion Containing Tetraethoxysilane in Organic Phase and 1M Hydrochloric Acid in Water Droplets Obtained in Synthesis Example 3 in 80 parts of chloroform Star-shaped poly (methyl oxazoline-phenyl oxazoline) (S-MO-
(co-PO) 1.5 parts was dissolved to prepare a chloroform solution of the star polymer. After dissolving 10 parts of tetraethoxysilane in this solution, 8 parts of a 1M aqueous HCl solution was added, and the mixture was stirred for 5 minutes to obtain a coffee-colored translucent inverted microemulsion liquid.

The reverse microemulsion was added at room temperature for 48 hours.
The mixture was allowed to stand for a time, and a sol-gel reaction of tetraethoxysilane was allowed to proceed. The insoluble particles generated in the reaction system were repeatedly washed with ethyl acetate, replaced with methanol, and repeatedly washed with a centrifugal separator to obtain light purple star polymer / silica hybrid fine particles. These fine particles emitted strong red fluorescence under visible light irradiation of a fluorescence microscope. Also, in the absorption spectra of these fine particles,
At the molecular level, a porphyrin-specific solle band and Q band appeared at 420, 518, 554, 592, and 647 nm, and in these fluorescence spectra, a porphyrin-derived fluorescence peak appeared at 649 nm by the excitation light of 420 nm.

Observation with a transmission electron microscope revealed that these were spherical fine particles. FIG. 2 shows a transmission electron micrograph. A cross-sectional photograph (not shown) of the spherical fine particles suggested that many hollow structures were contained therein, and the hollow inner diameter of the spherical particles was in the range of 22 to 25 nm. That is,
The inside of these spherical fine particles contains many spherical cavities of 30 nm or less, and the larger the diameter of the spherical fine particles, the larger the number of the cavities. Was 30 nm or less. FIG. 3 shows a schematic view of a transmission electron micrograph because the scanner reading of the transmission electron micrograph is unclear.

<Example 10> (Star polymer obtained by mixing two inverse microemulsions in which the compound dissolved in water droplets was cadmium chloride and sodium sulfide)
Synthesis of Cadmium Sulfide Hybrid Fine Particles) In 80 parts of chloroform, the star-shaped poly (methyloxazoline-phenyloxazoline) (S-MO-
(co-PO) 1.5 parts was dissolved to prepare a chloroform solution of the star polymer. To this solution, 8 parts of a 0.1 M cadmium chloride aqueous solution was added and stirred for 5 minutes to obtain a translucent inverse microemulsion liquid (A). In a similar manner, 8 parts of a 0.1 M aqueous sodium sulfide solution was added to a chloroform solution of the polymer to obtain a translucent inverse microemulsion liquid (B).

While the inverse emulsion (A) was vigorously stirred, the inverse emulsion (B) was added thereto, and stirring was continued at room temperature for 1 hour. Thereafter, the reaction solution was allowed to stand overnight. After the reaction solution was centrifuged and the supernatant was taken out, methanol was added to the remaining fine particles, and washing was repeated by centrifugation to obtain fine particles in which a star polymer and cadmium sulfide were hybridized. These fine particles exhibited a particle size of 20 to 100 nm. In addition, red fluorescence derived from porphyrin was observed from a fluorescence microscope of these fine particles.

[0120]

Industrial Applicability The present invention is directed to an inverse micropolymer of an amphiphilic star polymer having a porphyrin having a photofunction, a catalytic function, and a dye function in its central skeleton and containing various metal salts, water-soluble polymers or dyes. It is possible to provide fine particles comprising a composite of an amphiphilic star polymer and a metal oxide or metal salt, which are useful for a photocatalyst support and the like formed by a chemical reaction in an emulsion or the inverse microemulsion. .

The functional inverse microemulsion of the present invention is an inverse microemulsion provided with a porphyrin function by using an amphiphilic star polymer having porphyrin. The functional inverse microemulsion of the present invention contains, as its form, a metal alkoxide in an organic phase and various water-soluble compounds (metal salts, reducing agents, synthetic polymers, biopolymers) in water droplets. Inverse microemulsions can be easily prepared.

The functional inverse microemulsion and fine particles of the present invention are useful as nano- to micro-scale organic / inorganic hybrid fine-particle materials, and include oxidizing catalysts, photocatalysts, and porphyrins and metal salts contained therein.
It is useful in various applications such as a micro-actor, a photoelectric conversion element, a non-linear material, a solar cell, a gas sensor, a DNA sensor, and a photodynamic cancer diagnosis.

[Brief description of the drawings]

FIG. 1 shows the ternary composite fine particles obtained in Example 8 having a molecular weight of 10,000.
It is a transmission electron microscope photograph of 0 times. The horizontal line at the lower right of the photograph indicates a length corresponding to 250 nm in total length.

FIG. 2 is a transmission electron micrograph of fine particles comprising a composite of an amphiphilic star polymer and a metal oxide obtained in Example 9. The horizontal line at the lower right of the photograph is 5.0 μm in total length.
The length corresponding to m is shown.

FIG. 3 is a schematic view of a transmission electron micrograph showing a cross-sectional structure of a plurality of fine particles obtained in Example 9. The horizontal line at the lower right of the schematic diagram indicates a length corresponding to 1.0 μm in total length.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/26 C08K 3/26 3/28 3/28 3/30 3/30 3/32 3/32 3 / 38 3/38 5/057 5/057 5/09 5/09 5/19 5/19 5/3412 5/3412 C08L 101/14 C08L 101/14 C09B 67/46 C09B 67/46 Z C09C 1/40 C09C 1/40 3/10 3/10

Claims (16)

[Claims] Claims: 1. An amphiphilic polymer having an amphiphilic polymer represented by the general formula (I) as an arm and having a porphyrin or a metalloporphyrin as a central skeleton.
A functional inverse microemulsion characterized in that an aqueous liquid is dispersed in a hydrophobic oily medium. General formula (I) (Wherein P represents a linear polymer having an amphipathic property bonded to a benzene ring, M represents hydrogen or a metal atom, and the metal atom is iron, manganese, zinc, copper, tin, molybthenium, or ruthenium. Represents a transition metal such as, or a metal selected from rare earth metals such as europium and gadolinium, and n represents an integer of 1 to 3.) 2. The functional inverse microemulsion according to claim 1, wherein the hydrophobic oleaginous medium contains a metal alkoxide. 3. The functional inverse microemulsion according to claim 2, wherein the metal alkoxide is at least one compound selected from the group consisting of alkoxysilane, alkoxytitanium, alkoxyzircon and aluminum alkoxide. 4. The functional inverse microemulsion according to claim 1, wherein the aqueous liquid contains a water-soluble polymer. 5. The water-soluble polymer is at least one synthetic polymer selected from the group consisting of polymethacrylic acid, polyacrylic acid, polyacrylamides and polyoxazolines, or the water-soluble polymer is polypeptides, DNAs and the like. 5. The functional inverse microemulsion according to claim 4, wherein the functional inverse microemulsion is one or more biopolymers selected from the group consisting of polysaccharides. 6. The functional inverse microemulsion according to claim 1, wherein the aqueous liquid contains a water-soluble metal salt. 7. The metal of the water-soluble metal salt is calcium, barium, iron, manganese, zinc, copper, cadmium, palladium, platinum, molybdenum, ruthenium, silver,
The functional inverse microemulsion according to claim 6, which is a metal selected from the group consisting of gold, zirconium, cesium, iridium, europium, and gadolinium. 8. The functional inverse microemulsion according to claim 1, wherein the aqueous liquid contains an anionic compound or a water-soluble reducing agent compound. 9. The functional reverse micro of claim 8, wherein the anionic compound is a compound selected from the group consisting of sodium chloride, sodium bromide, sodium iodide, sodium carbonate, sodium phosphate and sodium sulphide. Emulsion. 10. The functional inverse microemulsion according to claim 8, wherein the water-soluble reducing agent compound is at least one compound selected from the group consisting of sodium borohydride, oxalic acid, sodium oxalate and hydrazine. 11. The functional inverse microemulsion according to claim 1, wherein the aqueous liquid contains a water-soluble dye. 12. The functional inverse microemulsion according to claim 11, wherein the water-soluble dye is at least one dye selected from the group consisting of rhodamines, porphyrins, phthalocyanines, and stilbazoles. 13. A composite of an amphiphilic star polymer and a metal oxide formed by a sol-gel reaction of a metal alkoxide in the functional inverse microemulsion according to claim 1. Fine particles consisting of 14. The metal oxide is silicon oxide, titanium oxide,
The fine particles comprising a composite of an amphiphilic star polymer and a metal oxide according to claim 13, which is at least one member selected from the group consisting of zircon oxide and aluminum oxide. 15. A composite of an amphiphilic star polymer and a metal salt, formed by an ion exchange reaction of a metal salt in the inverse microemulsion according to any one of claims 1 to 12. Fine particles. 16. The method according to claim 16, wherein the metal salt is calcium, barium,
Iron, manganese, zinc, copper, cadmium, palladium,
Platinum, molybdenum, ruthenium, silver, gold, zirconium, cesium, iridium, europium, a metal halide selected from the group consisting of gadolinium,
2. A metal which is a metal sulfide, a metal carbonate, or a metal phosphate.
Fine particles comprising a complex of the star polymer according to 5 and a metal salt.