JP2009079187A - Method for producing organic-inorganic composite - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a composite having a fine inorganic compound uniformly dispersed in a polymer by a simple synthesizing operation by cleaving a clay layer by removing alkali metal ions between clay layers simultaneously with synthesis of polyester or polyacidic anhydride. <P>SOLUTION: The method for producing an organic-inorganic composite comprises retaining an organic solvent solution 1 containing at least one compound a selected from the group consisting of a dihydric phenol compound, a dicarboxylic acid compound and a dicarboxylic anhydride (a), and an acid halide (b), and an aqueous solution 2 containing clay mineral in a state in which at least parts of the organic solvent solution 1 and the aqueous solution 2 are compatibilized, or making both the solutions coexist in a separated state, to generate an alkali metal salt of the compound (a) and to further react the alkali metal salt with the acid halide (b). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing an organic-inorganic composite comprising polyester or polyanhydride as a matrix polymer and clay mineral as an inorganic component.

  An organic-inorganic composite is a composite material in which an inorganic compound is dispersed in an organic polymer that serves as a matrix, and has attracted attention as a material that combines the processability and flexibility of organic polymers with the heat resistance and hardness of inorganic materials. ing. The method of using clay minerals as an inorganic component of such organic-inorganic composites has been widely studied, but inter alia, by combining an organic ammonium salt between clay layers to give clay an organic material affinity, There are very many studies of combining difficult organic materials and inorganic materials (clay minerals) (for example, Patent Documents 1 and 2). However, these methods require organic treatment of clay, which causes high costs. To organically treat clay minerals, clay minerals containing metal ions such as sodium are dispersed in water and swelled in water, and quaternary ammonium salts with organic chains are added in the form of aqueous solutions or organic solutions. After exchanging ions between layers, it is prepared by filtering and washing. Therefore, the material is certainly more expensive than a clay mineral having metal ions as a raw material between layers (usually 5000 yen / kg or more), and the organic-inorganic composite using this material as a raw material cannot be avoided. The reason why such treatment is essential is that metal ions between clay mineral layers such as sodium adversely affect the heat resistance of the polymer in addition to imparting affinity to the organic material to the clay mineral.

  On the other hand, an organic treatment is not performed, an inexpensive clay mineral having metal ions (particularly alkali metal ions) between layers is used as a composite raw material, and the alkali metal ions can be discharged to the outside of the composite upon synthesis. Patent Documents 3 and 4 disclose techniques for synthesizing composites with polyamide. These apply a polycondensation type reaction, and metal ions in the clay are removed by ion exchange of the amino group at the end of the polyamide. In particular, although not shown in Examples in Patent Document 3, an aqueous solution containing a diphenol monomer and a water-soluble or dispersible clay mineral as essential components, an acylated dicarboxylic acid monomer, and an organic solvent are essential. It is said that an organic-inorganic composite having polyester as an organic component can also be synthesized by bringing the organic solution phase into contact.

In the method of Patent Document 3, it is necessary to completely dissolve the diphenol monomer in the aqueous solution simultaneously with the clay mineral, but the diphenol monomer that can be used in this method originally has an aromatic ring such as water-soluble resorcinol or hydroquinone. There was only one monomer. General-purpose dihydric phenols such as bisphenol A are hardly dissolved in water at the same time as the clay mineral, so that it is difficult to obtain a substantial polymer, and the yield of the organic-inorganic composite obtained is extremely low.
JP-A-6-248176 JP-A-7-26123 JP-A-9-208291 Japanese Patent Laid-Open No. 11-236501

  The present invention uses an inexpensive clay mineral having polyester or polyanhydride as a matrix polymer and a metal ion (particularly alkali metal ion) between layers as a composite raw material, and while synthesizing the polymer, an alkali metal between clay layers A method is provided by which a complex in which fine inorganic compounds are uniformly dispersed in the polymer can be produced by a simple synthesis operation by cleaving the clay layer by removing ions.

  As a means for obtaining a composite in which a fine inorganic compound is uniformly dispersed in a polyester or polyanhydride, the present inventor previously described a dihydric phenol compound or dicarboxylic acid as a raw material for the polyester or polyanhydride. All monomers such as acid compounds and acid halides are dissolved in an organic solvent, and water-soluble metal compounds and alkali silicates containing alkali metals that are raw materials for inorganic compounds are dissolved in water. Each solution is at least partially compatible. Have found ways to keep them in a separated state or to coexist in a separated state.

  A dihydric phenol compound or dicarboxylic acid compound and an acid halide do not react in the absence of a base at ordinary temperature and pressure. That is, an organic solvent solution in which a dihydric phenol compound or dicarboxylic acid compound and an acid halide are dissolved does not react at room temperature and exists stably. On the other hand, clay minerals dispersed, swollen and dissolved in water are basically stable if the clay minerals are properly selected, and the aqueous solution becomes alkaline. By keeping these stable solutions coexisting at least partially in a compatible state or separated, alkali metal ions between the clay layers cause the hydroxy group of the dihydric phenol compound or the carboxy group of the dicarboxylic acid compound. A hydrogen atom dissociates as a hydrogen ion to cause an ion exchange reaction with an alkali metal ion, and a dihydric phenol compound or a dicarboxylic acid compound becomes an alkali metal salt. A dihydric phenol compound or dicarboxylic acid compound that has become an alkali metal salt significantly increases the reactivity, and a polymer can be formed by causing a polycondensation reaction with an acid halide. Furthermore, the clay mineral from which the alkali metal between the layers has been detached is cleaved by the repulsion between the layers due to the negative charge of the sheet constituting the layer, but it is finely surrounded by the polymer produced in this situation and fixed. And uniformly dispersed in an organic polymer such as polyester. In this case, the alkali metal ions removed from the clay mineral react with the halogen ions generated from the acid halide and are removed from the composite by dissolving in water in the form of an alkali halide such as NaCl. Presumed.

That is, the present invention provides an organic solvent solution (1) containing at least one compound (a) selected from the group consisting of a dihydric phenol compound, a dicarboxylic acid compound and a dicarboxylic acid anhydride, and an acid halide (b). ,
An aqueous solution (2) containing clay minerals,
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. Provided is a method for producing an organic-inorganic composite in which a metal salt is reacted with the acid halide (b).

According to the present invention, a general-purpose polymer such as polyester or polyanhydride is used as a matrix polymer, and at the same time, the clay mineral layer is peeled off while synthesizing the polymer. A composite in which minerals are dispersed can be produced by a simple synthetic operation and using an inexpensive clay mineral having metal ions between layers. Unlike the method of physically mixing clay minerals into organic polymers, the polymer is synthesized and compounded while separating the clay layers, resulting in a very fine composite of organic and inorganic components. It is done.
Further, the reaction can be carried out in a short step at ordinary temperature and pressure using a general-purpose stirring device.

(Method for producing organic-inorganic composite)
In the production method of the present invention, at least one compound (a) selected from the group consisting of a dihydric phenol compound, a dicarboxylic acid compound and a dicarboxylic acid anhydride and an aqueous solution (2) containing a clay mineral are stirred and mixed. Is due to.

(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), catechol (1,2-dihydroxybenzene) and the like. Can be mentioned.
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 ( Tetraphenol biphenol), bisphenol S, 4,4′-isopropylidenediphenol (bisphenol A), bisphenol compounds such as bisphenol H, bisphenol C, bisphenol E, 1,4-dihydroxynaphthalene, 1,5 -A compound having a naphthalene skeleton such as dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, etc., and any aromatic ring such as anthracene having three or more aromatic rings, regardless of the substitution site List compounds with two phenolic hydroxyl groups Can.

  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 hydrogen ion dissociation property of the hydroxyl group of the aliphatic alkyl diol compound is extremely lower than that of the dihydric phenol, so that the alkali metal ion in the clay mineral described later becomes an ion and an ion of the hydroxyl group of the aliphatic alkyl diol compound. This is probably because the exchange reaction 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))
(Clay mineral)
Since the clay mineral used in the present invention is dissolved in the aqueous solution (2) and used, it must be soluble, swellable, and dispersible in water. Further, a clay mineral having an alkali metal ion layer is preferable. Among them, a clay mineral in which the alkali metal is sodium is most preferably used because it is highly soluble in water and swellable and is inexpensive. These clay minerals swell or finely disperse in water and show alkalinity. This alkali metal between the clay layers facilitates the synthesis of the polymer.

  Particularly preferred as the clay structure is a smectite group, and among them, montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, stevensite and the like can be exemplified more specifically.

(Solvent of aqueous solution (2))
The clay mineral used in the present invention is dispersed, dissolved, or swollen 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 an organic polymer, you may dissolve basic substances, such as an alkali hydroxide and an alkali carbonate, in aqueous solution (2). Moreover, in order to improve mixing property with the organic solvent solution (1), additives such as a surfactant may be contained.

(Production method)
In the method for producing an organic-inorganic composite of the present invention, an organic solvent solution (1) containing the compound (a) and an acid halide (b) and an aqueous solution (2) containing a clay mineral are used as the organic solvent solution. (1) and at least a part of the aqueous solution (2) are kept in a compatible state or coexisted in a separated state to form an alkali metal salt of the compound (a), and further, the alkali metal salt and the It is characterized by reacting with an acid halide (b).
The synthesis mechanism of the organic-inorganic composite in 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 in the absence of a base at normal temperature and pressure. 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, aqueous solutions and dispersions of clay minerals are also stable for a certain period.
When these stable solutions are allowed to coexist in a state where at least a part thereof is compatible or separated, the alkali metal between the clay mineral layers causes a hydrogen atom of the hydroxy group or carboxy group of the compound (a). Dissociates as hydrogen ions and causes an ion exchange reaction with alkali metal ions, whereby 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 polymer such as polyester or polyanhydride. 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.

  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.

(Clay mineral delamination)
On the other hand, the clay mineral from which the alkali metal has been removed from the interlayer is finely dispersed in the synthetic system due to repulsion between the clay layers having negative charges. Although it is presumed that it is unstable as it is, a polymer such as polyester is synthesized around the clay layer and precipitated as a solid, so it is considered to be fixed in the organic polymer in a state where the layers are separated.

(Synthetic reaction field of organic-inorganic composite)
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 by interfacial polymerization, 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) may be charged simultaneously in 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 10 minutes or less, although it depends on the monomer species, reactor, 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 the present invention is not particularly limited as long as the production apparatus can satisfactorily contact and react the organic solvent solution (1) and the aqueous solution (2). Is 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.

(Addition of other inorganic components)
In the present invention, in addition to the clay mineral, the metal compound having at least one metal element containing at least one alkali metal selected from the group consisting of metal oxides, metal hydroxides and metal carbonates in the aqueous solution (2) (C-1) (hereinafter may be simply referred to as metal compound (c-1)) and / or metal silicate (c-2) or metal compound that dissolves in basic aqueous solution and precipitates in neutral solution (c- 3) may be contained. By containing these compounds in the aqueous solution (2), various inorganic components can be contained.

(Raw material of other components: 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, titanium. Sodium complex oxides such as sodium oxide, sodium vanadate, sodium tungstate, sodium zirconate, potassium zincate, potassium aluminate, potassium chromite, potassium molybdate, potassium stannate, potassium manganate, potassium tantalate , Potassium tellurite, potassium ferrate, potassium vanadate, potassium tungstate, potassium goldate, potassium silverate, potassium zirconate, etc., potassium aluminate, lithium aluminate, lithium molybdate, lithium stannate , Lithium manganate, lithium tantalite, lithium titanate, lithium vanadate, lithium tungstate, in addition rubidium compound oxide of the lithium composite oxide of lithium zirconate 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.

In the present invention, when the metal compound (c-1) is used in combination, the alkali metal in the metal compound (c-1) is used as a polymer synthesis accelerator such as polyester, like the alkali metal between the clay mineral layers. Thus, a metal compound having a metal element other than the alkali metal is precipitated. As an example, when sodium stannate (Na ₂ SnO ₃ ), which is a kind of alkali stannate, is used, SnO ₂ is compounded simultaneously with the clay mineral.

(Other components 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.

  In the present invention, when the alkali silicate (c-2) is used together, the alkali metal in the alkali silicate (c-2) is like a polymer synthesis accelerator such as polyester as in the case of the metal compound (c-1). Is used to remove silica (silicon oxide).

(Other components Metal compound (c-3))
There is a method of adding to the aqueous solution (2) a metal compound (c-3) that dissolves in a basic aqueous solution and precipitates in a neutral solution. This method utilizes the fact that the pH of the aqueous solution changes from basic to neutral as the polymer is synthesized. That is, since the aqueous solution is basic at the initial stage of the polymer formation reaction, the metal compound (c-3) remains in a dissolved state. However, when the organic-inorganic complexing reaction proceeds and the aqueous solution approaches neutrality, it easily precipitates. Thus, an organic-inorganic composite having a plurality of different inorganic compounds is obtained. Since the metal compound (c-3) precipitates due to a change in solubility in an aqueous solution due to pH and does not involve a chemical reaction, the metal compound (c-3) can be combined with the composition before the addition.

The amount of the metal compound (c-3) used in the present invention dissolved in the basic solution is 100 mg / L or more in a basic solution at a normal temperature of pH 13.
If the dissolved amount is smaller than this amount, the amount capable of sufficiently exerting the function of the metal compound cannot be supported in the form of fine particles on the composite.
In addition, the amount of the metal compound (c-3) used in the present invention dissolved in the neutral solution is 30 mg / L or less in a neutral aqueous solution at room temperature of pH 6-8. If the amount of dissolution is larger than this amount, the metal compound may flow out in the filtration or water washing steps after synthesis of the complex, resulting in low loading efficiency and difficulty in obtaining the desired loading amount. .

  As the metal species of the metal compound (c-3) used in the present invention, any metal can be used as long as it has a compound exhibiting the above-described solubility characteristics. Alkali metals and alkaline earth metals such as lithium, magnesium and calcium, transition metals such as titanium, manganese, iron, cobalt, nickel, copper, silver, gold, molybdenum, tungsten, palladium and ruthenium, aluminum, zinc, indium and tin Typical metals such as lead, antimony and the like can be exemplified. Among them, a transition metal element belonging to Group 3 to Group 12 of the periodic table or a typical metal element belonging to Groups 13 to 16 of the periodic table is preferably used. A composite compound containing two or more metal elements can also be used. In addition, as long as the compound species satisfies the above-mentioned solubility characteristics, oxides, halides, hydroxides, oxalates, carbonates, phosphates, perchlorates, etc. of various metals can be used without limitation. Can do. Therefore, in the present invention, a very wide variety of metal oxides can be easily supported.

Examples of metal compounds that can be suitably used as the metal compound (c-3) used in the present invention include alkali metals and alkaline earth metal compounds such as lithium phosphate and magnesium hydroxide, tungsten (VI) oxide, and vanadium oxide. (V), cobalt oxide (II), cobalt hydroxide (II), cobalt oxalate (II), niobium oxide (II), iron hydroxide (II), niobium oxide (V), molybdenum oxide (VI), water Manganese oxide (II), gold oxide (III), gold hydroxide (III), silver iodate (I), silver carbonate (I), silver oxide (I), silver sulfide (I), copper oxide (I), Copper hydroxide (II), basic copper carbonate (II), copper oxide (II), copper phosphate (II), copper oxalate (II), rhenium oxide (VI), palladium hydroxide (II), hydroxide Transition metal compounds such as ruthenium (IV), tin oxide (II), tin hydroxide (II), aluminum hydroxide, phosphorus Aluminum oxide, indium (III) hydroxide, nickel (II) oxalate, zinc (II) oxide, zinc (II) hydroxide, zinc (II) oxalate, antimony (III) oxide, gallium (III) oxide, oxidation Typical metal compounds such as lead (II), lead (IV) oxide, lead (II) phosphate, lead (II) hydroxide are listed. Since these metal compounds are dissolved in water and used, they may be hydrates. These can be used alone or in combination of two or more.

Hereinafter, the present invention will be described with specific examples, but the present invention is not limited thereto. Unless otherwise specified, “part” and “%” are based on mass.

(Example 1: Polyester / clay mineral composite)
(Composite synthesis process)
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 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 (1-1).
Next, 1.38 g of synthetic hectorite (chemical formula Na _0.33 (Mg _2.67 Li _0.33 ) Si ₄ O ₁₀ (OH) ₂ : “Lucentite SWN” manufactured by Co-op Chemical Co., Ltd.)) as a clay mineral and hydroxylated in 60 g of ion-exchanged water 1.37 g of sodium was added and stirred at room temperature for 15 minutes to obtain a translucent homogeneous transparent aqueous solution (2-1). 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 white product was generated as the aqueous solution (2-1) was dropped. In this state, stirring was continued for 30 minutes to obtain a slurry containing a white composite.

(Cleaning process of complex)
The slurry was placed on a 95 mmφ Nutsche filter paper having a mesh size of 4 μm and filtered under reduced pressure at 0.015 MPa to obtain a white pasty liquid-containing organic-inorganic composite. This powder was dispersed in 200 g of methanol and stirred at room temperature for 30 minutes to wash with methanol, and the dispersion was filtered by the same method as above to obtain a methanol-containing organic-inorganic composite. This was subsequently dispersed in 250 g of ion-exchanged water, washed with water by stirring at room temperature for 30 minutes, and the water-containing organic-inorganic composite was obtained by performing a water washing step of filtering the dispersion in the same manner as described above. Obtained. This was dried at 120 ° C. for 5 hours to obtain a white organic-inorganic composite.

(Example 2: Polyester / clay mineral composite)
3.78 g of 4,4′-isopropylidenediphenol (bisphenol A) as compound (a) was added to 85 g of anisole and stirred at room temperature for 5 minutes to completely dissolve it. Next, 3.37 g of isophthalic 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 (2-1). A white organic-inorganic composite was obtained by carrying out the same synthesis, washing, and drying treatment as in Example 1 except that this organic solvent solution was used.

(Example 3: Polyester / clay mineral composite)
By adding 10.82 g of the same clay mineral used in Example 1 to 80 g of ion-exchanged water and stirring, a translucent and viscous aqueous solution (3-2) was obtained. This aqueous solution was put into a 300 cm ³ stirring device having an anchor blade, and stirred at a blade rotation speed of 200 revolutions / minute at room temperature with the same structure as the organic solvent solution (1-1) over 1 minute. A certain organic solvent solution (3-1) was dropped and reacted. As the organic solvent solution (3-1) was added dropwise, a white product was generated. In this state, stirring was continued for 30 minutes to obtain a slurry containing a white composite. When the obtained slurry was washed, a gray organic-inorganic composite was obtained by performing the same washing and drying treatment as in Example 1 except that a 60 ° C. water washing step with 250 g of ion-exchanged water was added once last. Obtained.

(Example 4: polyanhydride / clay mineral complex)
To 53 g of tetrahydrofuran, 1.96 g of succinic acid as compound (a) was added and stirred at room temperature for 5 minutes to completely dissolve. Next, 3.37 g of isophthalic 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 (4-1). A white organic-inorganic composite was obtained by carrying out the same synthesis and washing treatment as in Example 1 except that this organic solvent solution was used.

(Example 5: polyanhydride / clay mineral complex)
Synthesis and washing similar to Example 1 except that the organic solvent solution (5-1) in which the compound (A) in the organic solvent solution (1-1) of Example 1 was changed to 1.66 g of succinic anhydride was used. By processing, a white organic-inorganic composite was obtained.

(Example 6: Polyester / clay mineral, tungsten oxide composite; combined use of metal compound (c-3))
An aqueous solution having the same composition as the aqueous solution (2-1) used in Example 1 was prepared. 0.10 g of tungsten oxide was put into the aqueous solution, and the tungsten oxide was dissolved by stirring under heating at 60 ° C. to obtain a translucent uniform aqueous solution (6-2). A white organic-inorganic composite was obtained by performing the same synthesis and washing treatment as in Example 1 except that this aqueous solution was used.

(Comparative Example 1)
3.78 g of 4,4′-isopropylidenediphenol (bisphenol A) was added to 60 g of water and stirred for 15 minutes at room temperature, but a white powder dispersion was obtained without dissolving.
Next, 1.38 g of the same clay mineral as used in Example 1 and 1.37 g of sodium hydroxide were added and stirred for 160 minutes at room temperature, but the white powder of bisphenol A was not completely dissolved. This white precipitate could not be dissolved by the treatment of heating the aqueous solution to 60 ° C. or the treatment of adding 50 g of water. Therefore, synthesis from a uniform solution (dispersion, swelling) raw material solution was abandoned.

(Comparative Example 2)
Using a resin melt kneading device, Labo Plast Mill C type, KF-15 mixer (Toyo Seiki Seisakusho Co., Ltd.), the following tests were conducted to knead and combine the resin and clay mineral by the melt kneading method. It was. 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”), clay mineral: in Example 1 1.75 g of the same clay mineral used

  The organic inorganic composites obtained in the above Examples and Comparative Example 2 were measured and tested for the following items.

(Measurement 1) Measurement method of ash content and calculation method of clay mineral content in the complex The organic-inorganic complex was thoroughly dried and then precisely weighed (complex mass), and this was increased in air at 5 ° C / min. The mixture was heated to 600 ° C. at a temperature rate and baked at the same temperature for 1 hour to completely burn off the polymer component, and the mass after calcination was measured to obtain the ash mass. In addition, when synthetic hectorite, which is an inorganic raw material used in the present invention, was baked alone under the same heating conditions, the residual weight was 85% by mass due to removal of crystal water of the clay mineral. Therefore, in the organic-inorganic composites having only clay mineral as an inorganic component in Examples 1 to 5, the clay mineral content in the composite is expressed by the following mathematical formula 1.

In addition, when an inorganic component other than clay mineral was introduced as the inorganic component of Example 6, the content of clay mineral was calculated from the ash content obtained in this measurement by the following formula. did.

This formula can calculate the inorganicity when inorganic components other than clay minerals are compounded by the same method as in the present invention (for example, the synthesis of a complex using a metal compound (c-3) as a raw material). This is because it is known that the yield almost coincides with the theoretical inorganic value.

(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. In addition, using the obtained results of total element analysis, give sample data of the sample for measurement (given data is sample shape; film, correction component: cellulose, mass value per area of actually measured sample) to the apparatus. By using the FP method (Fundamental Parameter method; a method in which the uniformity and surface smoothness of the sample is assumed and correction is performed using constants in the apparatus and the components are quantified), the element abundance ratio in the complex is calculated. .

In the samples obtained in any of the examples, magnesium and silicon, which are elements constituting the clay mineral, were detected, and it was shown that the target inorganic substance was complexed. On the other hand, among the elements constituting the clay mineral, it was confirmed that sodium, which is an element between the clay layers, was significantly reduced from the content in the original clay mineral.
The reduction rate of sodium at this time was calculated as the sodium removal rate from the following formula.

  On the other hand, in Example 6, it was shown that tungsten has a value almost equal to that estimated from the charged amounts of these raw materials.

(Measurement 3) Verification of organic polymer (Fliers conversion type infrared spectroscopic analysis: measurement of FT-IR)
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 to 3 and 6 to 8, Unitika “U-polymer U-100”, which is a bisphenol A type aromatic polyester (polyarylate), was used as a reference sample.
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 and 6, IR spectrum data having almost the same peak intensity was obtained at the same peak position as that of the reference sample. 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 organic 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. The obtained slices were each photographed at 500,000 times using TEM observation "JEM-2010EFE" (manufactured by JEOL Ltd.) which is an energy filter TEM capable of elemental mapping by EDS elemental analysis.
At this time, it is a clay mineral that is observed in a dark color with a high aspect ratio, and contains Mg specific to the clay mineral by element mapping, but these become flakes having a thickness of 50 nm or less, and more In the case where the thickness was not observed, it was determined that the dispersion state of the clay mineral was good (◯). On the other hand, when the clay mineral formed a coarse aggregate or a clay mineral having a thickness of 50 nm or more was observed, it was determined as (×).
In the case of a composite having two types of inorganic components, when an inorganic component derived from a component other than clay mineral is identified by element mapping, and there is no particle having a maximum side of 200 nm or more in any particle in the component. It was determined that the dispersed state of the inorganic component was good (◯). On the other hand, when particles having a maximum side of 200 nm or more were observed, it was determined as (×).

Table 1 below shows the results of evaluation of the organic-inorganic composite obtained in Example 1 and Comparative Example 2 where the inorganic components of Examples 1 to 5 were only clay minerals.

  Table 2 below shows the evaluation results of composites in which the inorganic component of Example 6 is composed of a clay mineral and a metal compound (c-3).

  As shown in Tables 1 and 2, an organic-inorganic composite in which the inorganic component is a clay mineral and the organic polymer component is polyester or polyanhydride is synthesized in a short time at normal temperature and normal pressure by the production method of the present invention. Could be obtained. In addition, most of the sodium ions, which are metal ions between the clay layers in the clay mineral in the obtained composite and can cause a decrease in the heat resistance of the polymer, were removed with the synthesis of the polymer. In addition, the dispersion of clay minerals was also good. Moreover, as shown in Table 2, the inorganic component (metal compound (c-3)) other than the clay mineral could be supported simultaneously by allowing the inorganic raw material to coexist in the aqueous solution (2).

  On the other hand, as shown in Comparative Example 1, divalent phenol as a raw material of polyester could not be uniformly dissolved in an alkaline aqueous solution containing clay mineral, and synthesis of the composite itself was impossible. Further, as shown in Comparative Example 2, in the test in which the clay mineral was directly melt-kneaded with the polyester, it was clear that the dispersion state of the clay mineral was poor and the sodium content in the clay mineral naturally remained. It became.

(Possibility of industrial use)
The composite of the present invention can be used as a structural material or a heat-resistant material having a reinforcing effect of inorganic components by processing such as molding by itself. Moreover, it can also be used as a high functional (heat resistance, strength, gas barrier property, etc.) material of the polymer by compounding it with a low polar polymer such as polyester by a method such as kneading.

Claims (2)

An organic solvent solution (1) containing at least one compound (a) selected from the group consisting of a dihydric phenol compound, a dicarboxylic acid compound and a dicarboxylic anhydride, and an acid halide (b);
An aqueous solution (2) containing clay minerals,
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. A method for producing an organic-inorganic composite comprising reacting a metal salt with the acid halide (b). The method for producing an organic-inorganic composite according to claim 1, wherein the aqueous solution (2) contains a metal compound (c-3) dissolved in a basic aqueous solution and precipitated in a neutral solution.