JP2009062407A - Method for producing organic-inorganic composite material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic-inorganic composite material formed with a plurality of inorganic materials. <P>SOLUTION: The method for producing an organic-inorganic composite material has a process 1 of making an organic solvent solution (1) containing a dihydric phenol compound, a dicarboxylic acid compound or a dicarboxylic anhydride and an acid halide and a basic aqueous solution (2) containing a metal compound and/or an alkali silicate having two or more metal elements containing an alkali metal and a metal compound containing a metal having a standard oxidation-reduction potential (E<SP>0</SP>) in an aqueous solution at 25°C of ≥-0.5 V, and allowing the aqueous solution (2) to coexist with the above organic solvent solution (1), to prepare an organic-inorganic composite material, and a process 2 of adding a reducing agent to a slurry containing the organic-inorganic composite material prepared by the process 1 and reducing a metal ion in the metal compound (c-3) into the metal on the organic-inorganic composite material. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing an organic-inorganic composite using polyester or polyanhydride as a matrix polymer, in which single metal fine particles such as noble metals are supported in a particulate form.

Dispersed and compounded inorganic fine particles in organic polymer for the purpose of imparting properties such as processability and flexibility of organic polymer and heat hardness and wear resistance of inorganic material such as surface hardness. Thus, studies for producing organic-inorganic composites have been widely conducted.
For example, the design of an organic-inorganic composite that takes advantage of the properties unique to inorganic materials can be expected to have a higher composite effect by combining inorganic fine particles having a particle size as small as possible with a high filling rate. This is because the smaller the particle size, the larger the surface area per weight of the inorganic fine particles, and the wider the interface region between the organic polymer and the inorganic material. Furthermore, when the filling rate of the inorganic fine particles is increased, the characteristics of the inorganic material can be enhanced.

  On the other hand, it can also be expected to obtain an organic-inorganic composite having various properties by combining a plurality of inorganic materials. For example, by combining an inorganic compound such as a metal oxide with a single metal, it has a metal-derived catalytic function in addition to properties specific to inorganic materials such as heat resistance, wear resistance, surface hardness, etc. A complex can be obtained.

  As an organic-inorganic composite obtained by complexing a metal as an inorganic material, for example, a polymer-metal cluster composite characterized by contacting a solid polymer compound with a vapor of a heavy metal compound at a temperature equal to or higher than its glass transition temperature is known. (See, for example, Patent Document 1). However, this method is a method in which an organic polymer and a single metal are complexed almost uniformly to the inside, and is a preferable method as a method for imparting various properties (optical properties, modifying properties, etc.) of the metal to the entire bulk of the material. However, a metal compound such as a metal oxide having a boiling point higher than that of a single metal cannot be compounded at the same time.

  On the other hand, organic-inorganic composites using oxides such as silicon oxide (silica) and aluminum oxide (alumina) as inorganic materials are known. The organic-inorganic composite may be, for example, a sol-gel method for synthesizing an organic-inorganic composite by hydrolyzing and dehydrating and condensing a metal alkoxide in the presence of an organic monomer (see, for example, Patent Document 2), or a resin melted by heating. It can be obtained by a melt-kneading method (see, for example, Patent Document 3) or an interfacial polymerization method (see, for example, Patent Documents 4 and 5) in which an organic / inorganic composite is produced by mixing and dispersing inorganic components.

  However, the sol-gel reaction described in Patent Document 2 has a drawback that metal oxides that can be supported are limited. A metal alkoxide is essential for the sol-gel reaction, but a noble metal with high stability generally does not form a metal alkoxide, and therefore cannot be combined even in the form of an oxide. Moreover, since the conversion rate to an oxide changes with the difference in the metal kind between the compounds which form an alkoxide, it is difficult to control these and to make multiple types complex. Moreover, since the sol-gel reaction requires a long time, there is a disadvantage that the production efficiency is low.

  Further, in the melt-kneading method represented by Patent Document 3, it is difficult to introduce an inorganic material in a dispersed state of 20% by mass or more in an organic polymer. In addition, it is difficult to uniformly disperse the metal oxides such as silicon oxide and aluminum oxide and a plurality of kinds of inorganic materials having different mixing characteristics into the resin, such as simple metal fine particles. In particular, it is known that the melting point is lowered due to the size effect when the single metal is a nanometer order fine particle, and there is a possibility that it will be fused and coarsened by the melt-kneading operation with the resin.

Further, the interfacial polymerization methods described in Patent Documents 4 and 5 are excellent in that a complex in which a fine inorganic compound is uniformly dispersed in a polymer can be combined with a plurality of types of inorganic compounds by a simple synthesis operation. Is the method. However, the polymer used as the matrix is limited to polyamide, polyurethane or polyurea.
JP 2000-256489 A JP-A-8-157735 JP 2003-170420 A JP 2005-048008 A JP 2005-068311 A

  The problem to be solved by the present invention is to provide an organic-inorganic composite in which a plurality of inorganic materials are composited. More specifically, a single metal fine particle such as a noble metal, polyester and metal oxide, etc. An organic-inorganic composite supported in the form of fine particles in an organic-inorganic composite comprising the above is provided by a simple method.

As a means for obtaining a composite in which a fine inorganic compound is uniformly dispersed in a polyester or polyanhydride, the present inventors previously obtained a dihydric phenol compound or a raw material for polyester or polyanhydride, All monomers such as dicarboxylic acid compounds and acid halides were dissolved in an organic solvent, a metal compound containing an alkali metal, which is a raw material for inorganic compounds, and an alkali silicate were dissolved in water, and each solution was at least partially compatible. We have found a way to keep it in a coexistent state or in a separated state.
The present inventors applied this, and further, in the aqueous solution, a metal compound (c-3) having a metal having a standard oxidation-reduction potential (E ⁰ ) at 25 ° C. in the aqueous solution of −0.5 V or more. Coexisting and maintaining the organic solvent solution and at least a part of the aqueous solution in a compatible state or coexisting in a separated state to obtain an organic-inorganic composite, and then reducing the slurry into the slurry containing the organic-inorganic composite Is added to the metal compound (c-3) to reduce the metal ion to a simple metal on the organic-inorganic composite. In addition, the inventors have found that an organic-inorganic composite supported by fine particles in an organic-inorganic composite comprising polyester and metal oxide in a uniformly dispersed state can be easily obtained, thereby solving the above-mentioned problems.

That is, the present invention provides an organic solvent solution (1) containing at least one compound (a) selected from the group consisting of a divalent phenol compound, a dicarboxylic acid compound and a dicarboxylic acid anhydride, and an acid halide (b). ), And a metal compound (c-1) and / or alkali silicate (c) having two or more metal elements including at least one alkali metal selected from the group consisting of metal oxides, metal hydroxides and metal carbonates -2) and a basic aqueous solution (2) containing a metal compound (c-3) having a metal having a standard oxidation-reduction potential (E ⁰ ) at 25 ° C. of −0.5 V or more in an aqueous solution. And coexisting in a state where at least a part of the organic solvent solution (1) and the aqueous solution (2) are compatible or separated from each other to produce an alkali metal salt of the compound (a), , Step 1 of obtaining an organic-inorganic composite by reacting an alkali metal salt with the acid halide (b), and adding a reducing agent to the slurry containing the organic-inorganic composite obtained in Step 1, a metal compound (c-3) And 2) reducing the metal ions in the metal-inorganic complex to a metal on the organic-inorganic complex.

In the production method of the present invention, a plurality of inorganic compounds such as a metal compound and a metal can be combined with polyester or polyanhydride.
In the production method of the present invention, since the inorganic compound is precipitated from a water-soluble state, it is difficult to form coarse particles. Therefore, an organic-inorganic composite in which nano-sized inorganic compounds are dispersed in polyester or polyanhydride can be obtained.
In addition, since the metal compound (c-3), which is a metal precursor, is preliminarily dissolved in the organic-inorganic composite synthesis system, the metal is deposited on the surface of the inorganic compound produced in Step 1 (ion In step 2 and reduced in step 2 by the added reducing agent. Thereby, it is possible to deposit fine particles and zero-valent metal. Both Step 1 and Step 2 can be carried out continuously without transfer, and are completed in a short time (basically less than 30 minutes) at room temperature and normal pressure, so the organic-inorganic composite of the present invention can be easily obtained. Can be obtained. In particular, when the reduction in step 2 is sufficiently performed, the metal can be supported on the organic-inorganic composite with a yield of almost 100% from the raw metal compound (c-3). By appropriately selecting the types and ratios of the raw material metal compound (c-1), alkali silicate (c-2) and metal compound (c-3), an organic-inorganic composite having various properties can be obtained. Is possible.

(Definition of words)
Hereinafter, the production method of the present invention will be described in detail. In the present invention, the “inorganic compound” is a generic term for non-metallic inorganic compounds such as silicon oxide, metal compounds such as aluminum oxide, and the like. The “metal compound” refers to a substance in which a metal and other elements such as a metal oxide, a metal hydroxide, and a metal carbonate are combined. “Metal” indicates a zero-valent simple metal.

(Method for producing organic-inorganic composite, step 1)
In the production method of the present invention, step 1 is a metal compound having two or more metal elements including polyester or polyanhydride and at least one alkali metal selected from the group consisting of metal hydroxide and metal carbonate ( c-1) is a step of synthesizing an organic-inorganic composite with an inorganic compound made from alkali silicate (c-2) as a raw material (hereinafter referred to as metal compound (c-1)). On the other hand, during the reaction, the metal compound (c-3) is adsorbed on the formed organic-inorganic composite.

(Organic solvent solution (1))
The organic solvent solution (1) used in the present invention comprises at least one compound (a) selected from the group consisting of a divalent phenol compound, a dicarboxylic acid compound and a dicarboxylic acid anhydride, and an acid halide (b). contains. A polyester or polyanhydride obtained by a polycondensation reaction between the compound (a) and the acid halide (b) serves as a matrix polymer. At this time, when a dihydric phenol compound is used as the compound (a) and a dicarboxylic acid halide is used as the acid halide (b), a polyester is obtained, and a dicarboxylic acid compound or a dicarboxylic acid anhydride is used as the compound (a). When a dicarboxylic acid halide is used as the acid halide (b), it becomes a polyanhydride. In the case of a polyacid anhydride, the dicarboxylic acid compound to be used is preferably an aromatic dicarboxylic acid compound, an aliphatic dicarboxylic acid compound, an aromatic dicarboxylic acid anhydride or an aliphatic dicarboxylic acid anhydride.

(Compound (a): Dihydric phenol compound)
The dihydric phenol compound used in the present invention is a compound having two phenolic hydroxyl groups that can be dissolved in an organic solvent simultaneously with an acid halide. Two phenolic hydroxyl groups may be on one aromatic ring or on a plurality of aromatic rings. These are appropriately determined depending on the properties of the desired polymer.
Examples of the compound having two phenolic hydroxyl groups on one aromatic ring include resorcin (1,3-dihydroxybenzene), hydroquinone (1,4-dihydroxybenzene), and catechol (1,2-dihydroxybenzene). It is done.
Examples of the compound having two phenolic hydroxyl groups on a plurality of aromatic rings include 2,2′-biphenol, 4,4′-biphenol, 3,3′-5,5′-tetramethylbiphenol ( Tetramethylbiphenol), bisphenol compounds such as bisphenol S, bisphenol A, bisphenol H, bisphenol C, bisphenol E, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, Examples of compounds having a naphthalene skeleton such as 2,6-dihydroxynaphthalene and compounds having two phenolic hydroxyl groups in any aromatic ring of any compound having three or more aromatic rings such as anthracene Can do.

  The dihydric phenol may have a substituent which does not react with the acid halide at room temperature and normal pressure and does not react with the organic solvent to be used or the aqueous solution (B) described later. Examples of such substituents include halogen elements and alkyl groups.

  In the present invention, an aliphatic alkyldiol compound such as ethylene glycol or 1,4-butanediol does not cause a polycondensation reaction with an acid halide. This is because the dissociation property of the hydrogen ion of the hydroxyl group of the aliphatic alkyldiol compound is extremely lower than that of the dihydric phenol, so that the alkali metal ion in the metal compound (c-1) or alkali silicate (c-2) described later is used. This is probably because the ion exchange reaction with the hydrogen ion of the hydroxyl group of the aliphatic alkyldiol compound is extremely slow.

(Compound (a): Dicarboxylic acid compound)
The dicarboxylic acid compound used in the present invention is a compound having two carboxy groups that can be dissolved in an organic solvent simultaneously with an acid halide. The dicarboxylic acid compound may be an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid.

  As the aromatic dicarboxylic acid compound, for example, as a compound composed of an aromatic ring, a compound having one aromatic ring such as terephthalic acid and isophthalic acid, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, A compound having a plurality of aromatic rings such as a compound having a naphthalene skeleton such as 1,6-dicarboxynaphthalene or 2,6-dicarboxynaphthalene, or a dicarboxylic acid having a biphenyl skeleton such as biphenyl-2,2′-dicarboxylic acid An acid etc. are mentioned.

Examples of the aliphatic dicarboxylic acid compound include ethanedioic acid (oxalic acid), propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), and hexanedioic acid (adipic acid). , Octanedioic acid (suberic acid), decanedioic acid (sebacic acid), and the like.
The dicarboxylic acid compound may have a substituent that does not react with the acid halide and does not react with the organic solvent to be used or the aqueous solution (B) described later. Examples of such substituents include halogen elements and alkyl groups.

(Compound (a): Dicarboxylic anhydride)
The dicarboxylic acid anhydride compound used in the present invention may be any compound as long as the acid anhydride bond is hydrolyzed to dicarboxylic acid in the presence of water and a base. For example, tetrahydrofuran-2,5-dione (succinic anhydride), glutaric anhydride and the like can be exemplified as the aliphatic dicarboxylic acid anhydride. In addition, aromatic dicarboxylic anhydrides such as phthalic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,8-naphthalic anhydride, and 1,2-naphthalic anhydride can be exemplified. These compounds may have a substituent that does not react with the acid halide and does not react with the organic solvent to be used or the aqueous solution (B) described later. Examples of such substituents include halogen elements and alkyl groups. Since the dicarboxylic acid anhydride has higher solubility in the organic solvent than the dicarboxylic acid compound, the concentration in the organic solvent solution (1) can be increased, and the reaction efficiency can be further increased.

(Acid halide (b))
The acid halide (b) used in the present invention does not react with a dihydric phenol compound, a dicarboxylic acid compound, or a dicarboxylic acid anhydride under normal temperature and normal pressure conditions in the organic solvent solution (1). If it is a compound which produces a polycondensation reaction for the first time by making it coexist with this, it will not specifically limit.
For example, examples of the acid halide (b) having an aromatic group include isophthalic acid chloride, terephthalic acid chloride, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene composed of two or more aromatic rings, Acid halides such as 1,6-dicarboxynaphthalene and 2,6-dicarboxynaphthalene. Since these aromatic acid halides are strong against hydrolysis reaction with water constituting the aqueous solution (2), the yield can be increased even when a solvent compatible with water is used as the organic solvent. Preferably used.
Examples of the acid halide (b) having an aliphatic group include acid halides such as succinic acid, adipic acid, azelaic acid, and sebacic acid.
The acid halide (b) may have a substituent that does not react with an organic solvent or an aqueous solution (B) described later. Examples of such substituents include halogen elements and alkyl groups.

(Organic solvent)
The compound (a) and the acid halide (b) are both used as an organic solvent solution (1) dissolved in an organic solvent. The organic solvent that can be used is not particularly limited as long as it can be dissolved without reacting with either the compound (a) or the acid halide (b). Specific examples include ethers such as tetrahydrofuran, dimethyl ether, diethyl ether, n-butyl ether and anisole, ketones such as acetone, 2-butanone and cyclohexanone, and acetic acid such as ethyl acid acid, propyl acetate and butyl acetate. Examples thereof include halogenated hydrocarbons such as alkyl, chloroform and methylene chloride, and propylene carbonate. In addition, aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons such as n-hexane are very low in polarity, so the polarity of the compound (a) is large due to the large hydrocarbon moiety, and it is completely dissolved. Can be used only when

When a water-soluble or water-soluble organic solvent such as tetrahydrofuran, dimethyl ether, acetone, ethyl acetate or the like is used as the organic solvent, the resulting organic solvent solution (1) and the aqueous solution (2) described below are compatible with each other. The reaction proceeds by solution polymerization in a solution having a uniform reaction field, and the resulting organic-inorganic composite becomes powdery.
On the other hand, when an organic solvent that is hardly water-soluble or water-insoluble, such as dibutyl ether, anisole, butyl acetate, chloroform, methylene chloride, is used, the resulting organic solvent solution (1) is separated from the aqueous solution (2) described later. The reaction proceeds by interfacial polymerization in which the reaction field is an interface between water and an organic solvent, and the resulting organic-inorganic composite becomes a lump.

The molar ratio of the compound (a) to the acid halide (b) in the organic solvent solution (1) is not particularly limited as long as the synthesis reaction of the organic-inorganic complex proceeds normally, but the reaction proceeds in a high yield. Is preferably approximately 1: 1.
The monomer concentrations of the compound (a) and the acid halide (b) in the organic solvent solution (1) in the present invention are not particularly limited as long as the polymerization reaction proceeds sufficiently. From the viewpoint of good contact, a concentration range of 0.01 to 3 mol / L, particularly 0.05 to 1 mol / L is preferable.
Moreover, you may add suitably the additive which does not inhibit other reaction to the said organic solvent solution (1).

(Aqueous solution (2))
The basic aqueous solution (2) used in the present invention is a metal compound having two or more metal elements selected from the group consisting of metal oxides, metal hydroxides and metal carbonates and containing at least one alkali metal ( c-1) (hereinafter abbreviated as metal compound (c-1)) and / or alkali silicate (c-2), and the standard oxidation-reduction potential (E ⁰ ) at 25 ° C. in an aqueous solution is −0.5 V or more. And a metal compound (c-3) having a certain metal.

  The raw material of the inorganic compound of the organic-inorganic composite obtained in the present invention is the metal compound (c-1) and / or alkali silicate (c-2). When the metal compound (c-1) is used as a raw material, a metal compound having a metal element other than an alkali metal is precipitated. When an alkali silicate (c-2) is used as a raw material, silica (silicon dioxide) is precipitated.

(Metal compound (c-1))
The metal compound (c-1) used in the present invention is specifically represented by the following general formula (1).

In the general formula (1), A represents an alkali metal element, M represents a metal element other than an alkali metal, and B represents an oxygen atom, a carboxy group, or a hydroxy group. x, y, and z are numbers that allow A, M, and B to be combined independently. (Since there are many non-stoichiometric compounds (for example, Na _1.6 Al _0.9 O _2.8 ) in complex oxide-based inorganic materials, neither xyz can be defined as an integer or a decimal. Therefore, it indicates a number that can exist stably. .)
The compound represented by the general formula (1) is preferably a compound that is completely or partially dissolved in water and exhibits basicity. And it is preferable that the metal compound which precipitates is a compound which hardly melt | dissolves in water.

  Examples of the compound in which B in the general formula (1) is an oxygen atom include sodium zincate, sodium aluminate, sodium chromite, sodium molybdate, sodium stannate, sodium tantalate, sodium tellurite, vanadium. Sodium complex oxides such as sodium oxalate, sodium tungstate and sodium zirconate, potassium zincate, potassium aluminate, potassium chromite, potassium molybdate, potassium stannate, potassium manganate, potassium tantalate, tellurite Potassium complex oxides such as potassium, potassium ferrate, potassium vanadate, potassium tungstate, potassium goldate, potassium silverate, and potassium zirconate, lithium aluminate, lithium molybdate, lithium stannate, lithium manganate , Lithium tantalate, lithium vanadate, addition rubidium compound oxide of the lithium composite oxide of lithium tungstate, and the like.

Examples of the metal compound (c-1) in which B in the general formula (1) includes both a carboxy group and a hydroxy group include zinc carbonate potassium, nickel carbonate potassium, potassium zirconium carbonate, cobalt carbonate potassium, and tin carbonate potassium. Is mentioned.
The metal compound (c-1) may be a hydrate in order to be dissolved in water. Moreover, each can also be used individually or in combination of 2 or more types.

  Among metal compounds (c-1), alkali aluminate, alkali stannate, alkali zincate, and zirconium carbonate alkali are particularly preferably used. Since these metal compounds have high water solubility and strong basicity when dissolved, the polycondensation reaction of the polymer serving as the matrix tends to proceed. Of these, alkali aluminates are most preferably used because they are particularly water-soluble and inexpensive.

(Alkali silicate (c-2))
The alkali silicate (c-2) used in the present invention is a composition formula of M ₂ O · nSiO ₂ in which sodium silicate (water glass) No. 1, No. 2, No. 3, No. 4 is an example, and M is Alkali metals, those having an average value of n of 1.8 to 4 can be mentioned. Further, sodium orthosilicate or sodium metasilicate whose average value of n is 1.8 or less and M is sodium, or sodium silicate is changed to another alkali metal, lithium silicate, potassium silicate, rubidium silicate. Etc. can also be used. Moreover, these can also be used in combination with a metal compound (c-1).

(Metal compound (c-3))
The metal compound (c-3) used in the present invention is a metal compound having a water-soluble metal having a standard oxidation-reduction potential (E ⁰ ) at 25 ° C. in an aqueous solution of −0.5 V or more. (Hereinafter, the metal deposited by reduction of the metal compound (c-3) is referred to as metal (c-3).)
The metal compound (c-3) is present on the organic-inorganic composite produced in Step 1, and in Step 2 described later, the obtained organic-inorganic composite is precipitated by reduction treatment to form a metal (c- 3).
Specific examples of the metal compound (c-3) include iron, indium, cobalt, nickel, molybdenum, tin, lead, rhenium, bismuth, copper, ruthenium, rhodium, silver, palladium, iridium from the one having a lower oxidation-reduction potential. , Platinum or gold perchloric acid, perbromic acid, perhalogenated acid such as periodic acid, halides such as chloride and bromide, oxides, hydroxides and the like, and metal compounds (c-1 ) Or alkali silicate (c-2), and any material that can maintain a dissolved state in an aqueous solution is not particularly limited. However, since the aqueous solution (2) is basic, when the aqueous solution of the metal compound (c-3) is acidic, it reacts with the metal compound (c-1) or the alkali silicate (c-2) in the aqueous solution (2). In addition, since an organic-inorganic composite synthesis reaction may be inhibited, an aqueous solution in which the metal compound (c-3) is dissolved alone is preferably basic or neutral.

In particular, since the reduction treatment in an aqueous solution is easy and the application range of the obtained metal-supported organic-inorganic composite is wide, preferred metal compounds (c-3) include rhenium, copper, ruthenium, rhodium, silver, Examples thereof include metal compounds containing a metal having a standard oxidation-reduction potential (E ⁰ ) of 0 V or more, such as palladium, iridium, platinum, and gold.

In addition, since noble metals have insufficient water solubility with the above metal compounds, it may be difficult to increase the loading amount. In this case, in order to make the aqueous solution neutral or basic while increasing the water solubility, the metal compound (c-3) is a compound that forms a metal complex containing an alkali metal or an ammonium salt. Is particularly preferred.
Such compounds are exemplified below.

Palladium compounds include potassium potassium cyanide, sodium palladium chloride, ammonium hexachloropalladium (IV), potassium hexachloropalladium (IV), sodium hexachloropalladium (IV), palladium (II) ammonium chloride, tetrachloropalladium (II ) Lithium,
Platinum compounds include sodium hexachloroplatinate (VI), potassium hexachloroplatinate (VI), ammonium hexachloroplatinate (VI), sodium tetochloroplatinate (II), ammonium tetochloroplatinate (II), disodium platinum cyanide , Platinum platinum cyanide, platinum rubidium cyanide, platinum cesium cyanide,
Examples of rhodium compounds include ammonium hexachlororhodium (III), sodium hexachlororhodium (III), and rhodium potassium cyanide.
As the iridium compound, ammonium hexachloroiridium (IV), sodium hexachloroiridium (III), ammonium hexachloroiridium (III), tripotassium iridium cyanide,
As the osmium compound, sodium hexachloroosmium (IV) acid, ammonium hexachloroosmium (IV) acid, potassium osmate,
Ruthenium compounds include ruthenium pentachloride diammonium, ruthenium triammonium chloride, hexaammineruthenium chloride, potassium ruthenate, and ruthenium potassium cyanide.
Examples of the gold compound include sodium tetochloroaurate (III), potassium tetochloroaurate (III) potassium dibasic sodium cyanide, potassium niobium cyanide,
Examples of the silver compound include potassium potassium cyanide.
These may be used alone or in combination of two or more. By using two or more kinds in combination, two or more kinds of metals can be supported. Further, since the metal compound (c-3) is used after dissolved in water, a hydrate is also preferably used.

(Solvent of aqueous solution (2))
The metal compound (c-1), the alkali silicate (c-2), and the metal compound (c-3) are dissolved in water and used as an aqueous solution (2). When the reaction with the organic solvent solution is desired to be carried out in a compatible state, a polar organic solvent such as acetone or tetrahydrofuran is mixed up to about 30% by mass of the aqueous solution (2) to adjust the solubility. May be.

  Moreover, in order to accelerate | stimulate the synthesis | combination of polyester or polyanhydride, you may dissolve basic substances, such as an alkali hydroxide and an alkali carbonate, in the said aqueous solution (2). Moreover, in order to improve mixing property with the said organic solvent solution (1), you may contain additives, such as surfactant.

(Synthesis mechanism of organic-inorganic composite in step 1)
The synthesis mechanism of the organic-inorganic composite of the present invention is estimated as follows.

(Synthesis reaction of polymer used as matrix)
As described above, the compound (a) and the acid halide (b) do not react under normal temperature and normal pressure in the absence of a base. That is, the organic solvent solution in which the compound (a) and the acid halide (b) are dissolved does not react at room temperature and exists stably. On the other hand, the aqueous solution of the metal compound (c-1) or the alkali silicate (c-2) is also stable.
When these stable solutions are allowed to coexist in a state where at least a part thereof is in a compatible state or separated, the compound can be obtained by the alkali metal of the metal compound (c-1) or the alkali silicate (c-2). The hydrogen ion of the hydroxy group or carboxy group in (a) is dissociated to cause an ion exchange reaction with the alkali metal ion, and the compound (a) becomes an alkali metal salt. The compound (a), which has become an alkali metal salt, is remarkably increased in reactivity, and a polycondensation reaction with the acid halide (b) is started to produce a polyester or polyanhydride polymer. Specifically, it is as follows (hereinafter, the case of a sodium metal salt is described as an alkali metal salt).

  When the compound (a) is a dihydric phenol, the hydrogen atom of the phenolic hydroxyl group is dissociated as a hydrogen ion and ion-exchanged with a sodium ion to produce an -ONa group. On the other hand, when the compound (a) is a dicarboxylic acid compound or a carboxylic acid anhydride, the hydrogen atom of the carboxy group is dissociated as a hydrogen ion and ion-exchanged with a sodium ion to generate -COONa.

  The compound (a) thus converted into an alkali metal salt significantly increases the reactivity, thereby causing a polycondensation reaction with the acid halide (b). When dihydric phenol is used as the compound (a), When the polyester uses a dicarboxylic acid compound or a dicarboxylic acid anhydride, a polyacid anhydride is generated. Alkali halides such as NaCl generated at this time are discharged out of the synthesis system by dissolving in water in the synthesis system or water in the washing step.

(Precipitation reaction of inorganic compounds)
On the other hand, the metal compound (c-1) or alkali silicate (c-2) from which the alkali metal has been released causes a sol-gel reaction to precipitate an inorganic compound. For example, when sodium silicate is used, -Si-ONa becomes a silanol group (-Si-OH) during the ion exchange reaction. A plurality of the generated silanol groups associate to cause a dehydration polycondensation reaction to form a (—Si—O—Si—) bond. Thereby, silica solidifies and precipitates.

  The polymer synthesis reaction and the inorganic compound precipitation reaction occur simultaneously during the ion exchange reaction with the precursors of the respective reactions. Therefore, it is considered that only one of the reactions does not occur unilaterally and proceeds almost simultaneously. Since the inorganic compound is simultaneously deposited while the polymer is synthesized, a composite in which the fine inorganic compound is uniformly dispersed in the polymer can be obtained by a simple synthesis operation.

The reaction field of the synthesis reaction differs depending on whether the organic solvent solution (1) and the aqueous solution (2) are compatible or incompatible.
As described above, when an organic solvent that is water-soluble or water-soluble, such as tetrahydrofuran, dimethyl ether, acetone, or ethyl acetate, is used as the organic solvent, the obtained organic solvent solution (1) and an aqueous solution (2) described later are obtained. The reaction occurs in a compatible state, the reaction proceeds by solution polymerization in a solution having a uniform reaction field, and the resulting organic-inorganic composite becomes powdery. Many of the polymers obtained at this time have a low molecular weight.
On the other hand, as described above, when an organic solvent that is hardly water-soluble or water-insoluble, such as dibutyl ether, anisole, butyl acetate, chloroform, methylene chloride, is used, an organic solvent solution (1) to be obtained and an aqueous solution (2) to be described later are obtained. Will coexist and react in a separated state. At this time, if the reaction field is an interface between water and an organic solvent, the reaction proceeds in an interfacial polymerization manner, and the resulting organic-inorganic composite is in the form of lumps to coarse particles. Many of the polymers obtained at this time have a high molecular weight.
These polymerization methods are not particularly limited, and can be selected depending on the desired shape of the organic-inorganic composite, the molecular weight of the polymer, and the like.

(Method for coexistence of organic solvent solution (1) and aqueous solution (2))
In order for the organic solvent solution (1) and the aqueous solution (2) to coexist in a state where at least a part thereof is compatible or separated, the organic solvent solution (1) and the aqueous solution (2) are in contact with each other. The organic solvent solution (1) and the aqueous solution (2) are usually charged into one reaction kettle having a stirring blade. The reaction temperature does not need to be set particularly high. For example, the reaction proceeds sufficiently in a temperature range of about −10 to 50 ° C. near room temperature. Further, pressurization and decompression are not particularly required. The synthesis reaction of the organic-inorganic composite is usually completed in a short time of 30 minutes or less, although it depends on the monomer species, reaction apparatus, and scale used.

  Specifically, the other solution may be added to the reaction kettle charged with the organic solvent solution (1) or the aqueous solution (2) while stirring. The order of charging the organic solvent solution (1) and the aqueous solution (2) is not particularly limited, but more preferably, the aqueous solution (2) while stirring in the reaction kettle charged with the organic solvent solution (1). ) And adding the aqueous solution (2) gradually, there is a risk that the ester part or the acid anhydride part of the polyester or polyanhydride that is the polymer component of the obtained organic-inorganic composite will be cleaved. Therefore, a good organic-inorganic composite can be obtained. This is because the ester site and acid anhydride site may be cleaved in the presence of an alkaline aqueous solution, so that the aqueous solution (2) showing alkalinity and the produced polyester or polyanhydride do not contact for a long time. is there.

(Manufacturing equipment)
The production apparatus used in Step 1 is not particularly limited as long as it is a production apparatus that can satisfactorily contact and react the organic solvent solution (1) and the aqueous solution (2). This method is also possible. Specific equipment for continuous operation is “Fine Flow Mill FM-15” manufactured by Taihei Koki Co., Ltd., “Spiral Pin Mixer SPM-15” manufactured by the same company, or INDAG Machinenbaugmb. "Dynamic mixer DLM / S215 type" etc. are mentioned. In the case of the batch type, since it is necessary to make good contact between the organic solution and the aqueous solution, it is preferable to use a stirrer having a strong stirring force such as an anchor blade, a max blend blade or a fowler blade.

(Step of reducing metal ions on organic-inorganic composite to metal (Step 2))
Step 2 of the present invention, that is, the reduction treatment operation, is performed by adding an aqueous solution of a reducing agent to the slurry in which the organic-inorganic composite synthesized in Step 1 is dispersed and stirring. This operation is not particularly limited as long as the reducing agent and the organic-inorganic composite slurry in which metal ions derived from the metal compound (c-3) are present are in sufficient contact. The temperature of the reduction treatment is not particularly limited as long as the reduction reaction occurs in water. If the metal (c-3) is a noble metal that can be easily reduced, a metal ion can be reduced to a metal by stirring within 30 minutes at room temperature by selecting an appropriate reducing agent. If the reduction reaction is difficult to occur because the standard oxidation-reduction potential (E ⁰ ) to be reduced is low, the temperature may be increased to several tens of degrees and the reduction treatment may be performed for a longer time.

(Reducing agent)
The reducing agent used in the present invention can be used without limitation as long as it can reduce metal ions derived from the metal compound (c-3) dissolved in the aqueous solution to the metal (c-3). . Examples of reducing agents include metal compounds having metal ions in a low valence state such as Fe (II), Sn (II), Ti (III), Cr (II), and organic compounds having a low degree of oxidation. In addition to aldehydes such as formaldehyde and acetaldehyde, carboxylic acids such as acetic acid and formic acid, oxalic acid, saccharides, dihydric phenols such as hydroquinone and catechol, sodium hypophosphite, sodium stearate, dithione Examples thereof include sodium acid, sodium bisulfite, hydrazine, ammonia and various amine compounds.

  The reducing agent acts on a precursor metal ion derived from the metal compound (c-3) present on the organic-inorganic composite dispersed in water obtained in Step 1, and this is converted into a metal ( Since it is necessary to reduce to c-3), it must be compatible with water. In the case of a liquid such as formaldehyde, acetaldehyde, hydrazine (hydrate) or the like, a direct or water dilution may be introduced into the organic-inorganic composite slurry. In addition, it is preferable to use a solid reducing agent by dissolving it in water before adding it to the organic-inorganic composite slurry because the reduction treatment can be performed quickly and uniformly. The concentration of the reducing agent in the aqueous solution may be appropriately selected depending on the metal species to be reduced and the amount of supported metal.

  In addition, complexing agents, buffering agents, brighteners, surfactants, etc., which are known and commonly used chemicals used in plating technology in aqueous solutions of organic-inorganic composite slurries and reducing agents in order to perform reduction to metals satisfactorily May be used.

The apparatus used in Step 2 in the present invention, that is, the metal reduction process is not particularly limited as long as it is a production apparatus that can satisfactorily contact and react the organic-inorganic composite slurry and the reducing agent solution. Either method is possible. When the standard oxidation-reduction potential (E ⁰ ) of the metal compound (c-3) to be used is high and a reducing agent having a strong reducing power is used, the reduction reaction is fast, so that it was used for the synthesis of the complex. A similar continuous stirrer can be used. In other cases, a general-purpose batch stirrer is preferable because stirring is performed for a sufficient time. In the production method according to the present invention, the metal (c-3) is supported at a yield of almost 100% except when the reducing agent is extremely insufficient or when the reducing conditions are not suitable for the metal to be reduced. be able to.

(Inorganic component of organic-inorganic composite)
In the organic-inorganic composite obtained by the production method of the present invention, the inorganic component is, as described above, fine particles of an inorganic compound derived from the metal compound (c-1) and / or alkali silicate (c-2) (hereinafter, the above-mentioned Inorganic compound derived from metal compound (c-1) is referred to as inorganic compound (c-1), inorganic compound derived from alkali silicate (c-2) is referred to as inorganic compound (c-2), and the fine particles The metal compound (c-3) supported on the metal is reduced to metal (c-3) fine particles.
For example, when the metal compound (c-1) is used as a raw material, the inorganic component is a metal oxide such as aluminum oxide (alumina), zirconium oxide, tin oxide, or zinc oxide. When alkali silicate (c-2) is used, silicon dioxide (silica) is obtained. Among these, aluminum oxide (alumina) and silicon dioxide (silica) are particularly preferable because the particle size of the obtained inorganic compound tends to be small and is easily combined. For example, when used as a heat resistance imparting agent or a dimensional stability imparting agent, it is preferable that the inorganic particle size is as small as possible to obtain a high effect. For example, if the average particle size is 500 nm or less, a higher effect is obtained.

(Contents of inorganic compound (c-1) and inorganic compound (c-2) with respect to 100% by mass of organic-inorganic composite)
The inorganic compound (c-1) and the inorganic compound (c-2) impart characteristics such as heat resistance and wear resistance of the inorganic material, such as surface hardness, and further support the metal (c-3). Also has a role.
Therefore, the content of the inorganic compound (c-1) and the inorganic compound (c-2) with respect to 100% by mass of the total amount of the organic-inorganic composite is preferably a certain value or more, more preferably 10 to 80% by mass, Preferably it is 20-80 mass%, Most preferably, it is 30-80 mass%. If the inorganic compound content is too high, on the contrary, sheet processing, processability to laminates, etc. and kneadability to resin may be impaired.

(Content of metal (c-3) with respect to 100% by mass of organic / inorganic composite)
The content of metal (c-3), that is, the supported amount, is not particularly limited as long as it is appropriately selected depending on the use of the obtained organic-inorganic composite. However, since the metal (c-3) is supported on the surface of the inorganic compound (c-1) and / or the inorganic compound (c-2), the inorganic compound (c-1) and / or the above-mentioned A smaller amount than the inorganic compound (c-2) is practical. Specifically, it is preferable that a maximum amount of about 15% by mass is supported with respect to 100% by mass of the total amount of the organic-inorganic composite.
Since the metal (c-3) is supported in a nano size, the supporting effect is high, and depending on the use, it may function if supported by 0.01% by mass or more, but a particularly preferable range is 0.1% by mass to 10%. % By mass.

The amount of the metal (c-3) supported is governed by the amount of the metal compound (c-3) dissolved in the aqueous solution (2). For example, when it is desired to increase the supported amount, a metal having a high water solubility is selected as the metal compound (c-3) to be used, and a large amount is dissolved in the aqueous solution (2) to perform step 1 and reduction in step 2 In the process, a sufficient reducing agent may be supplied.

(Shape of organic-inorganic composite)
The shape of the organic-inorganic composite to be obtained is not particularly limited, and may be obtained in a powder form or a bulk form depending on the production method and raw materials used. Specifically, the type of monomer for synthesizing the organic polymer, the effect of the compatibility of the organic solution (A) in water, and the influence of the shearing treatment of the complex in the synthesis process are large, and these should be changed. Can be designed.

  Hereinafter, the present invention will be described with specific examples, but the present invention is not limited thereto.

Example 1
(Synthesis process: Process 1)
3.78 g of 4,4′-isopropylidenediphenol (bisphenol A) as compound (a) was added to 50 g of acetone and stirred at room temperature for 5 minutes to completely dissolve it. Next, 3.37 g of terephthalic acid chloride was added as an acid halide (b) and stirred at room temperature for 5 minutes to obtain a light yellow transparent uniform organic solvent solution (1-1). Next, 11.55 g of water glass No. 3 as alkali silicate (c-2) is added to 27 g of ion-exchanged water and stirred at room temperature for 5 minutes, and another ion-exchanged water 27. By adding 0.486 g of hexachloroplatinum sodium hexahydrate as a metal compound (c-3) to 0 g and mixing with a yellow transparent aqueous solution which can be stirred for 15 minutes at room temperature, a pale yellow transparent aqueous solution (2- 1) was obtained.
Next, the organic solvent solution (1-1) was placed in a 300 cm ³ stirring device having an anchor blade, and the aqueous solution (2- 1) was dropped and reacted. A pale yellow product was generated as the aqueous solution (2) was added dropwise. In this state, stirring was continued for 15 minutes to obtain a slurry containing a light yellow powdery composite.

(Reduction process: Process 2)
The slurry was transferred to a 200 cm ³ beaker, and after stirring, a magnetic stirrer was stirred at room temperature, and 4 g of a reducing agent aqueous solution mixed with 5 g of hydrazine monohydrate and 10 g of ion-exchanged water was collected. It was dripped in 5 seconds. Immediately after dropping the reducing agent aqueous solution, the composite slurry around the dripping site gradually turned black and became uniform gray in 20 minutes. This color change indicates that platinum ions on the composite were reduced to platinum metal by the addition of a reducing agent.

(Cleaning process of complex)
This slurry was placed on a 95 mmφ Nutsche filter paper having an opening of 4 μm and filtered under reduced pressure at 0.015 MPa to obtain a gray paste-like liquid-containing organic-inorganic composite. This powder was dispersed in a liquid for mixing 100 g of methanol and 100 g of ion-exchanged water, stirred for 30 minutes at room temperature, washed with methanol / water, and the dispersion was filtered by the same method as above to contain water. / Methanol organic-inorganic composite was obtained. This was subsequently dispersed in 250 g of distilled water, washed with water by stirring for 30 minutes at room temperature, and the dispersion was filtered by the same method as above to obtain a water-containing organic-inorganic composite. This was dried at 120 ° C. for 5 hours to obtain a gray organic-inorganic composite.
In each example, the filtrate of the slurry after the reduction treatment was collected and then dried with hot air at 150 ° C. for 5 hours, and the remaining powder was subjected to fluorescent X-ray measurement described later.

(Example 2)
3.78 g of 4,4′-isopropylidenediphenol (bisphenol A) as compound (a) was added to 80 g of anisole and stirred at room temperature for 5 minutes for complete dissolution. Next, 3.37 g of terephthalic acid chloride was added as an acid halide (b) and stirred at room temperature for 5 minutes to obtain a light yellow transparent uniform organic solvent solution (1-2). Next, 2.97 g of powdered sodium aluminate P-100 manufactured by Asada Chemical Industry Co., Ltd. was added as a metal compound (c-1) to 27 g of ion-exchanged water and stirred for 10 minutes at room temperature to obtain a transparent light yellow Add 0.610 g of sodium palladium chloride dihydrate as the metal compound (c-3) to 27.0 g of ion-exchanged water and stir at room temperature for 15 minutes, and mix the obtained brown transparent aqueous solution with the aqueous solution. As a result, a light brown transparent aqueous solution (2-2) was obtained. A white organic-inorganic composite was obtained by the same synthetic operation as in Example 1 except that the adjusted organic solvent solution (1-2) and the aqueous solution (2-2) were used and the stirring time was 30 minutes. The composite particles in this slurry were slightly larger than Example 1 because anisole incompatible with water was used for the organic solvent solution.
Subsequently, 5 g of sodium phosphinate was added to 10 g of ion-exchanged water, and 6 g of the reducing agent solution obtained by dissolution by stirring at room temperature for 5 minutes was added as a reducing agent to the composite slurry, and 30 minutes at room temperature. The reduction process was performed by stirring. As the palladium was reduced by this treatment, the color of the composite slurry changed to gray.
This slurry was washed and dried in the same manner as in Example 1 to obtain a gray organic-inorganic composite.

(Example 3)
The 4,4′-isopropylidenediphenol (bisphenol A) in the organic solvent solution (1-1) in Example 1 was changed to 4.01 g of 3,3′-5,5′-tetramethylbiphenol (tetramethylbiphenol). The organic solvent solution (1-3) was prepared by changing 3.37 g of terephthalic acid chloride to the same amount of isophthalic acid chloride. Next, 27 g of ion-exchanged water was charged with 10.9 g of a zirconium potassium carbonate aqueous solution “Zirmel 1000” manufactured by Nippon Light Metal Co., Ltd. as a metal compound (c-1), and stirred at room temperature for 10 minutes. By adding 0.92 g of cupric chloride dihydrate as metal compound (c-3) to another 27.0 g of ion-exchanged water and stirring for 15 minutes at room temperature, mixing with the obtained blue transparent aqueous solution. A blue transparent aqueous solution (2-3) was obtained. A slurry containing a blue powdery organic-inorganic composite was obtained by the same synthesis operation as in Example 1 except that the adjusted organic solvent solution (1-3) and the aqueous solution (2-3) were used. To this slurry, 17 g of a reducing agent aqueous solution in which 10 g of hydrazine monohydrate and 10 g of ion-exchanged water were mixed was added, and reduction treatment was performed by stirring at room temperature for 60 minutes. As the copper was reduced by this treatment, the color of the composite slurry changed to brown.
This slurry was washed and dried in the same manner as in Example 1 to obtain a brown organic-inorganic composite.

Example 4
To 96 g of tetrahydrofuran, 1.96 g of succinic acid as a compound (a) was added and stirred at room temperature for 10 minutes to be completely dissolved. Next, 3.37 g of terephthalic acid chloride was added as an acid halide (b) and stirred at room temperature for 5 minutes to obtain a transparent and uniform organic solvent solution (1-4). Next, 11.55 g of water glass 3 as alkali silicate (c-2) is added to 27 g of ion-exchanged water and stirred at room temperature for 5 minutes to obtain a homogeneous transparent aqueous solution and another ion-exchanged water of 27.0 g. A transparent aqueous solution (2-4) was obtained by mixing 0.400 g of silver perchlorate as the metal compound (c-3) and mixing with a transparent aqueous solution obtained by stirring for 15 minutes at room temperature. A white organic-inorganic composite was obtained by the same synthetic operation as in Example 1 except that the adjusted organic solvent solution (1-4) and the aqueous solution (2-4) were used.
Subsequently, 5 g of sodium phosphinate was added to 10 g of ion-exchanged water, and 6 g of the reducing agent solution obtained by dissolving by stirring for 5 minutes at room temperature was added to the composite slurry as a reducing agent. Reduction treatment was performed by stirring for a minute. The color of the composite slurry changed to gray as silver was reduced by this treatment. The slurry was washed and dried in the same manner as in Example 1 to obtain a gray organic-inorganic composite.

(Example 5)
Except that the organic solvent solution (1-5) in which the succinic acid in the organic solvent solution (1-4) of Example 4 was changed to 1.66 g of succinic anhydride and the solvent was changed from tetrahydrofuran to 50 g of acetone was prepared, By performing the same synthesis, reduction, washing, and drying treatment as in Example 4, a gray organic-inorganic composite was obtained.

(Comparative example)
A test for kneading silicon dioxide fine particles and Cu fine particles by a melt kneading method under the following conditions using a lab plast mill C type, KF-15 mixer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), which is a resin melt kneading apparatus. went.
Heating temperature 320 ° C., mixer rotation speed 300 rpm, kneading time 10 minutes, mixed test product: 7.0 g of polyarylate (aromatic polyester) resin (U-polymer “U-100, manufactured by Unitika”), nano-silicon dioxide fine particles (Cai Kasei) Manufactured, average particle size 25 nm) 4.8 g, fine silver powder 0.20 g (average particle size 1 μm)
In addition, it was not possible to obtain a material having a purity of 1 μm or less for the single metal fine particles having a high purity except for the shape of the solvent dispersion.
In this method, introduction of silicon dioxide fine particles into the apparatus was somewhat difficult due to scattering of inorganic fine particles. Further, the thickening of the molten resin was remarkable and the kneading process was difficult.

  The following items were measured and tested for the organic-inorganic composites obtained in the above examples.

(Measurement 1) Measuring method of content ratio of inorganic compound The organic-inorganic composite was completely dried and then precisely weighed (composite mass), and this was baked in air at 600 ° C. for 1 hour to completely burn out the polymer components and baked. The latter mass was measured and used as the ash mass. The ash content was calculated from the following formula.

この時、金属（ｃ−３）は後述の濾液中の金属化合物の分析により収率がほぼ１００％であることより複合体中の存在量は金属化合物（ｃ−３）の量より既知である。従って、

At this time, the amount of the metal (c-3) in the complex is known from the amount of the metal compound (c-3) because the yield of the metal (c-3) is almost 100% according to the analysis of the metal compound in the filtrate described later. . Therefore,

が成り立つ。

Holds.

(Measurement 2) Verification of inorganic components (measurement with fluorescent X-rays)
About 1 g of the organic-inorganic composite powder was set in a measurement holder having an opening of 10 mm in diameter, and used as a measurement sample. The sample was subjected to total elemental analysis using a fluorescent X-ray analyzer “ZSX100e” manufactured by RIKEN ELECTRIC CO., LTD. Using the results of the total elemental analysis obtained, the sample data of the sample for measurement (the data given is sample shape; film, correction component; cellulose, mass value per area of the measured sample) is given to the apparatus, The element presence ratio in the complex was calculated by the FP method (Fundamental Parameter method; a method in which the uniformity of the sample and surface smoothness are assumed, and correction is performed using constants in the apparatus to quantify the components).

The organic-inorganic composite obtained in any of the examples is also an inorganic element derived from the metal compound (c-1) and / or alkali silicate (c-2) (in the case of sodium silicate, silicon, sodium aluminate). A large amount of aluminum and zirconium in the case of potassium zirconium carbonate was detected, indicating that the target inorganic compound was complexed. Metal (c-3) (Pt, Pd, Ag, Cu) was also detected. In the samples obtained in any of the examples, the amount of the metal (c-3) obtained by this method was within the error range of 0.2% by mass, and the metal compound (c-3) into the aqueous solution (2). It was consistent with the predicted value calculated from the amount charged.
On the other hand, the alkali (sodium in the case of sodium silicate and sodium aluminate, potassium in the case of potassium zirconium carbonate) derived from the metal compound (c-1) and / or alkali silicate (c-2), which are inorganic raw materials, is a trace. Only a degree was detected. Therefore, the ash (that is, the inorganic substance) obtained by the method for measuring inorganic compound fine particles (a) does not substantially contain an alkali metal. In the present invention, the metal compound (c-1) or the alkali silicate ( It was revealed that the alkali metal removal and solidification reaction from c-2) was performed according to the predicted reaction mechanism.
In addition, only the impurity elements such as Fe are detected in addition to the reaction by-products NaCl and KCl, and the metal element corresponding to the metal (c-3) is detected from the dried filtrate of each example. Was not. This showed that the metal compound (c-3) was all reduced by the reducing agent.

(Measurement 3) Verification of polyesters and polyanhydrides (Fourier transform infrared spectroscopy: FT-IR measurement)
A sample obtained by mixing and pulverizing powder of the obtained organic-inorganic composite with KBr powder was prepared, and measurement was performed by FT-IR (FT / IR-550 manufactured by JASCO Corporation) by the KBr disk method.
In Examples 1 and 2, Unitika “U-polymer U-100”, which is a bisphenol A type aromatic polyester (polyarylate), was used as a reference sample. In Example 3, "N-80" manufactured by Dainippon Ink & Chemicals, Inc., which is an aromatic polyester (polyarylate) of 3,3'-5,5'-tetramethylbiphenol (tetramethylbiphenol) type, is used. It was.
On the other hand, since there is no suitable reference sample for the composite having the polyanhydride as the organic polymer component in Examples 4 and 5, 1800 cm corresponding to C = O stretching characteristic of acid anhydride bond in IR measurement. Verification was performed by observing the presence and the intensity of the peak in the vicinity of ^-1 .

As a result, in Examples 1 to 3, IR spectral data having almost the same peak intensity was obtained at the same peak position as that of the reference sample in any of the examples. In Examples 4 and 5, a clear peak specific to an acid anhydride bond was observed in the vicinity of 1800 cm ⁻¹ in any of the examples. As a result, it was shown that the synthesis of the polymer was satisfactorily performed in any of the examples.

(Transmission electron microscope (TEM) observation and element mapping)
The organic-inorganic composite was hot-pressed for 2 hours under the conditions of 170 ° C. and 20 MPa / cm ² to obtain a flake made of an organic-inorganic composite having a thickness of about 1 mm. This was made into an ultrathin slice having a thickness of 75 nm using a focused ion beam apparatus. Based on TEM photographs of 500,000 times each, using “JEM-2010EFE” (manufactured by JEOL Ltd.), which is an energy filter TEM capable of elemental mapping by EDS elemental analysis simultaneously with TEM observation of the obtained sections. Elemental mapping was performed. The inorganic compound (c-1) and / or the inorganic compound (c-2) and the metal (c-3) were discriminated from the element type indicated by the mapping. By this element mapping, particle size measurement of inorganic compound (c-1) and / or inorganic compound (c-2), metal (c-3) described later (measurement 4), and metal (c-) described later (measurement 5). The supporting state of 3) on the inorganic compound (c-1) and / or the inorganic compound (c-2) was observed.

(Measurement 4) Particle size measurement of inorganic compound (c-1), inorganic compound (c-2), metal (c-3) Inorganic compound (c-1), inorganic compound (c-2), or metal (c As for the particle size of -3), 100 particle sizes were measured from a TEM photograph, and the average value was defined as the average particle size. In addition, the measuring method of the particle size was performed as follows according to the particle shape.
When the particles are substantially spherical: The length of an arbitrary side is defined as the particle size of the particles. When the inorganic compound (c-1) and / or the inorganic compound (c-2) was silicon dioxide or zirconium oxide, all metals (c-3) in Examples and Comparative Examples were measured by this method.
When the particles have an aspect ratio of 2 or more: The lengths of the major axis and minor axis of the particle were measured, and the value of (major axis + minor axis) / 2 was defined as the particle diameter of the particle. When the inorganic compound (c-1) was aluminum oxide, it was measured by this method.

(Measurement 5) Confirmation of the presence or absence of aggregates on the surface of the metal (c-3) Samples obtained by depositing carbon with a thickness of 10 nm on the organic-inorganic composite particles in each Example and Comparative Example, Elemental mapping for the metal (c-3) was performed using an electrolytic emission scanning electron microscope “SEM-EDX” manufactured by Hitachi, and the dispersion state of the supported metal was measured. The resolution of the metal size in this measurement method is 1 μm. When coarse particles of 1 μm or more were produced, there was an agglomerate, and there was no agglomerate if there was.

  Table 1 below shows the composition of the raw material solutions used in the tests of the examples. The upper row of the organic solvent solution (1) column is the acid halide (b), and the lower row is the compound (a). The upper row of the aqueous solution (2) column is the metal compound (c-1) or (c-2), and the lower row is the metal compound (c-3).

  Table 2 below summarizes the results of Examples 1 to 5 and Table 3 summarizes the above measurement results of the comparative examples.

  As a result, in the organic-inorganic composites obtained in Examples 1 to 5, each inorganic compound was dispersed in polyester or polyanhydride with a size of 250 nm or less and a high content of 20% by mass or more, and metal (C-3) was an extremely small particle size of 100 nm or less, and was dispersed without constituting an aggregate having a particle size of 1 μm or more. Almost no alkali metal was detected.

  On the other hand, in Comparative Example 1, although silicon dioxide powder having an average particle diameter of 25 nm was used as the inorganic compound (c-1), aggregation occurred in the kneading step, and nano-size composite could not be performed. . In addition, the metal (c-3) was not nano-sized due to the absence of nanoparticles and the use of micron-order particles, and aggregation was also observed.

  The organic-inorganic composite obtained in the present invention can be processed by a process such as molding. When a noble metal is supported, the reaction catalyst member and the environmental catalyst member are supported. It can be used for anti-mold members. Further, the obtained organic-inorganic composite is melt-kneaded and added to another resin, whereby the strength, elastic modulus, and impact resistance of the inorganic compound (c-1) or inorganic compound (c-2) are added to the resin. It is also possible to simultaneously impart properties such as conductivity, electronic conductivity, antistatic properties, and the like, as well as catalytic properties and antibacterial and antifungal properties due to the metal (c-3).

Claims (1)

An organic solvent solution (1) containing at least one compound (a) selected from the group consisting of a divalent phenol compound, a dicarboxylic acid compound and a dicarboxylic acid anhydride, and an acid halide (b);
Metal compound (c-1) and / or alkali silicate (c-2) having two or more metal elements containing at least one alkali metal selected from the group consisting of metal oxide, metal hydroxide and metal carbonate And a basic aqueous solution (2) containing a metal compound (c-3) having a metal having a standard oxidation-reduction potential (E ⁰ ) at 25 ° C. in an aqueous solution of −0.5 V or more,
An alkali metal salt of the compound (a) is produced by keeping at least a part of the organic solvent solution (1) and the aqueous solution (2) in a compatible state or in a separated state. Reacting a metal salt with the acid halide (b) to obtain an organic-inorganic composite;
Adding a reducing agent to the slurry containing the organic-inorganic composite obtained in Step 1, and reducing the metal ions in the metal compound (c-3) to metal on the organic-inorganic composite; A method for producing an inorganic composite.