JP2005036211A - Organic/inorganic composite and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic/inorganic composite having functions of both an organic material and various metal compounds, and its production method. <P>SOLUTION: The organic/inorganic composite comprises at least one organic polymer selected from the group consisting of a polyamide, a polyurethane and a polyurea, and at least one type of inorganic compound micro-particles which are finely dispersed in a matrix of the organic polymer and selected from the group consisting of periodic table group 3-12 transition metal elements and periodic table group 13-16 typical metal element metal oxides, metal hydroxides and metal carbonates. Wherein the inorganic compound micro-particles have ≤1 μm average particle diameter and 20-80 mass% content ratio in 100 mass% of the composite. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to an organic-inorganic composite containing an inorganic compound and a method for producing the same.

  Inorganic fine particles such as silica, alumina, titania, zirconia, etc. for the purpose of imparting the properties such as processability and flexibility of organic polymers and the properties of inorganic compounds such as heat resistance and wear resistance and surface hardness. Compounding within an organic polymer has been widely studied. In order to sufficiently exhibit the effect of compounding by this method, it is preferable to compound inorganic fine particles having a particle size as small as possible with a high filling rate. When the particle size of the inorganic fine particles is reduced, the surface area per weight of the inorganic fine particles is increased, and the interface region between the organic material and the inorganic fine particles is widened, so that a high reinforcing effect can be expected (area effect). In addition, as the filling rate of the inorganic fine particles increases, the compounding effect naturally increases (volume effect). However, if inorganic particles having a small particle size are combined with an organic polymer at a high filling rate, the dispersibility of the inorganic particles in the organic polymer is deteriorated, the cohesiveness is increased, and the desired properties cannot be obtained. There was a problem.

  In addition, since inorganic particles are essentially different from organic polymers in terms of surface characteristics, specific gravity, heat insolubility, and chemical insolubility, it is extremely difficult to make inorganic particles uniformly dispersed at a high filling rate. In addition, nanometer-order inorganic fine particles are usually expensive and may be scattered, resulting in poor handling. Further, even if an attempt is made to forcibly mix inorganic fine particles into an organic matrix using a large-sized disperser such as an extruder, a large amount of heat energy is required (see, for example, Patent Document 1). In Example 1 of Patent Document 1, a melt-kneading process at 200 ° C. is performed.

  On the other hand, using a so-called sol-gel method in which a metal alkoxide is hydrolyzed and polycondensed to form a metal oxide, a method of combining a nanometer-order metal oxide with an organic polymer has been widely studied ( For example, see Patent Documents 2 and 3.) In this method, uniform fine dispersion of the metal compound in the organic polymer is easy, and the polycondensation reaction occurs at a relatively low temperature of about room temperature to 150 ° C., which is advantageous in terms of energy. However, since the hydrolysis and polycondensation reactions each take a long time, there is a problem that the production efficiency is extremely low. In Example 1 of Patent Document 2, after stirring for 48 hours at room temperature for hydrolysis, polycondensation requires 21 hours at around 100 ° C. Similarly, in Patent Document 3, each reaction takes one day at room temperature and one day at 80 ° C.

  Moreover, in order to obtain an organic-inorganic composite by a sol-gel method, a metal alkoxide capable of causing a sol-gel reaction is essential. Therefore, complexation itself is impossible with a metal species that does not form an alkoxide. In addition, since metal alkoxides are generally expensive materials, it is inevitable to increase the price of the composite.

  Moreover, the manufacturing method of the composite_body | complex of polyamide and glass is known (for example, refer patent document 4). In the invention described in Patent Document 4, an aqueous phase (A) containing water, water glass, and a diamine monomer is brought into contact with an organic solvent phase (B) containing an organic solvent and an acylated dicarboxylic acid monomer. By causing the monomer polycondensation reaction at the interface, a composite of glass and polyamide can be easily produced using inexpensive water glass. However, since only the glass can be introduced into the polyamide as an inorganic composition according to the present invention, the functions that can be imparted to the composite are limited to thermal and mechanical stability, and other functions can be imparted. There wasn't.

JP-A-6-279615 JP-A-8-157735 JP-A-8-319362 Japanese Patent Laid-Open No. 10-176106

  The problem to be solved by the present invention is to provide an organic-inorganic composite of an organic polymer and an inorganic compound in which particles of the inorganic compound are uniformly finely dispersed at a high content in the organic polymer. Moreover, it is providing the easy manufacturing method of this organic inorganic composite.

The present inventors include an organic solution (A) in which at least one compound selected from the group consisting of a dicarboxylic acid halide, a dichloroformate compound, and a phosgene compound is dissolved in an organic solvent,
From the group consisting of metal oxides, metal hydroxides and metal carbonates of at least one alkali metal element and a transition metal element of Group 3 to Group 12 of the periodic table or a typical metal element of Groups 13 to 16 of the periodic table A composite of an organic polymer and various types of metal compounds (hereinafter referred to as organic-inorganic composite) by mixing and stirring and reacting at least one selected metal compound and a basic aqueous solution (B) containing diamine. This organic-inorganic composite is uniformly fine-dispersed with a high content of nanometer-sized inorganic compounds in organic polymers. As a result, the present invention has been completed.

That is, the present invention comprises at least one organic polymer selected from the group consisting of polyamide, polyurethane and polyurea,
From metal oxides, metal hydroxides and metal carbonates of transition metal elements of Group 3 to Group 12 of the periodic table or typical metal elements of Groups 13 to 16 of the periodic table finely dispersed in the matrix of the organic polymer An organic-inorganic composite comprising at least one inorganic compound fine particle selected from the group consisting of: an inorganic compound fine particle having an average particle diameter of 1 μm or less; and the inorganic compound fine particle in 100% by mass of the composite. An organic-inorganic composite having a content of 20 to 80% by mass is provided.

In the organic-inorganic composite of the present invention, the inorganic compound is finely dispersed in the nanometer order in the organic polymer matrix. Moreover, there is also much content of an inorganic compound. Therefore, the moldability and flexibility of organic materials and the functions of various metal compounds (for example, hardness, catalytic ability, insulation, semiconductivity, electronic conductivity, ionic conductivity, high specific surface area, high heat resistance, wear resistance) And organic / inorganic composites having dimensional stability against temperature change and moisture absorption).

The present invention also provides an organic solution (A) in which at least one compound selected from the group consisting of a dicarboxylic acid halide, a dichloroformate compound and a phosgene compound is dissolved in an organic solvent;
From the group consisting of metal oxides, metal hydroxides and metal carbonates of at least one alkali metal element and a transition metal element of Group 3 to Group 12 of the periodic table or a typical metal element of Groups 13 to 16 of the periodic table Provided is a method for producing an organic-inorganic composite in which at least one selected metal compound and a basic aqueous solution (B) containing a diamine are mixed and stirred and reacted.

An organic-inorganic composite having both moldability and flexibility of an organic material and functions of various metal compounds can be provided.

The present invention is described in further detail below.
The organic-inorganic composite of the present invention includes an organic solution (A) in which at least one compound selected from the group consisting of a dicarboxylic acid halide, a dichloroformate compound, and a phosgene compound is dissolved in an organic solvent;
From the group consisting of metal oxides, metal hydroxides and metal carbonates of at least one alkali metal element and a transition metal element of Group 3 to Group 12 of the periodic table or a typical metal element of Groups 13 to 16 of the periodic table It can be obtained by bringing at least one selected metal compound (hereinafter referred to as metal compound (1)) into contact with a basic aqueous solution (B) containing diamine and conducting a polycondensation reaction.

In this production method, the monomer in the organic solution (A) and the diamine in the aqueous solution (B) react rapidly by a stirring operation at room temperature and normal pressure for about 10 seconds to several minutes, and the yield of the organic polymer is high. can get. At that time, the alkali metal in the metal compound (1) acts as a removing agent for the hydrogen halide generated during the polymerization to accelerate the polymerization reaction of the organic polymer, and at the same time, the alkali metal in the metal compound (1). A metal compound having a metal element other than the element (hereinafter referred to as metal compound (2)) is converted into a solid. At that time, since the polymerization reaction of the organic polymer and the conversion of the metal compound (2) to the solid occur in parallel without generating either one, the organic-inorganic composite in which the metal compound fine particles are finely dispersed in the organic polymer. The body is obtained.

(Organic solvent used for organic solution (A))
When an organic solvent incompatible with water is used as the organic solvent used in the organic solution (A), the resulting polycondensation reaction is an interfacial polycondensation reaction that occurs only at the interface between the organic solution (A) and the aqueous solution (B). Become. In this case, since the molecular weight of the obtained organic polymer can be easily increased, a fiber-shaped composite is easily obtained. Moreover, a high-strength long fiber can also be obtained by carrying out spinning while pulling up the composite film formed at the interface between the organic solution (A) and the aqueous solution (B).
On the other hand, when an organic solvent that is compatible with water is used as the organic solvent, since polymerization occurs in a state where the organic solvent and water are emulsified, a powder-shaped composite can be easily obtained.

As an organic solvent used in the organic solution (A) in the present invention, any solvent that does not react with the various monomers and diamines in the organic solution (A) and dissolves the various monomers in the organic solution (A) can be used. It can be used without particular limitation. Among these, organic solvents incompatible with water include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as n-hexane, halogenated hydrocarbons such as chloroform and methylene chloride, and fats such as cyclohexane. Cyclic hydrocarbons can be mentioned.
Moreover, as an organic solvent compatible with water, ethers, such as tetrahydrofuran, ketones, such as methyl ketone and methyl ethyl ketone, can be mentioned as a typical example.

(Dicarboxylic acid halide)
Examples of the dicarboxylic acid halide used in the organic solution (A) in the present invention include acid halides of aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, and sebacic acid, and aromatics such as isophthalic acid and terephthalic acid. Examples include acid halides of dicarboxylic acids, or acid halides of aromatic dicarboxylic acids obtained by substituting hydrogen of these aromatic rings with halogen atoms, nitro groups, alkyl groups, and the like. These can be used alone or in combination of two or more. In particular, when an acid halide of an aliphatic dicarboxylic acid such as adipoyl chloride, azela oil chloride, or seba silk chloride is used, a fibrous organic-inorganic composite can be easily obtained. It can also be processed into a nonwoven fabric or the like.

(Dichloroformate compound)
Examples of the dichloroformate compound used in the organic solution (A) in the present invention include 1.2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8- Aliphatic diols such as octanediol, resorcin (1,3-dihydroxybenzene), hydroquinone (1,4-dihydroxybenzene), 1,6-dihydroxy having two or more hydroxyl groups on one or more aromatic rings Mention may be made of all the hydroxyl groups of dihydric phenols such as naphthalene, 2,2′-biphenol, bisphenol S, bisphenol A, tetramethylbiphenol, etc., which have been chloroformated by phosgenation treatment. These can be used alone or in combination of two or more.

(Phosgene compounds)
Examples of the phosgene compound used in the organic solution (A) in the present invention include phosgene, diphosgene and triphosgene. These may be used alone or in combination of both species.

  In the present invention, the matrix organic polymer of the organic-inorganic composite can be changed by selecting the monomer used in the organic solution (A). Polyamide can be obtained by reaction with an aqueous solution (B) when a dicarboxylic acid halide is used as a monomer, a polyurethane when a dichloroformate compound is used, or a polyurea when a phosgene compound is used. it can.

(Diamine)
As the diamine used in the aqueous solution (B) in the present invention, any diamine can be used without particular limitation as long as it reacts with each monomer in the organic solution (A) to produce an organic polymer, and 1,2-diaminoethane. 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane and other aliphatic diamines, m-xylylenediamine, p-xylylenediamine, m-phenylenediamine , P-phenylenediamine, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene and other aromatic diamines, or hydrogen of these aromatic rings as halogen atoms, nitro groups, alkyl groups, etc. Examples include substituted aromatic diamines. You may use these individually or in combination of 2 or more types. In particular, when an aliphatic diamine such as 1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminohexane is used, a fibrous organic-inorganic composite can be easily obtained and applied to a nonwoven fabric or the like. This is particularly preferable because it can be processed.

  The monomer concentration in the organic solution (A) and the aqueous solution (B) in the present invention is not particularly limited as long as the polymerization reaction proceeds sufficiently, but from the viewpoint of bringing the monomers into good contact with each other, 0.01 to 3 A concentration range of mol / L is preferable, and 0.05 to 1 mol / L is particularly preferable.

  The organic-inorganic composite of the present invention can have a pulp shape. The pulp shape is preferably a pulp shape having a fiber diameter of 20 μm or less and an aspect ratio of 10 or more.

The organic-inorganic composite of the present invention is a metal oxide or metal water of a transition metal element of Group 3 to Group 12 of the periodic table or a group of typical metal elements of Groups 13 to 16 of the periodic table, which is finely dispersed in an organic polymer matrix. It has fine particles of at least one inorganic compound selected from the group consisting of oxides and metal carbonates.

The transition metal element mentioned here means a transition metal element in a broad sense including Group 11 and Group 12 of the periodic table including copper and zinc. Specifically, the transition metal elements of Groups 3 to 12 of the periodic table referred to in the present invention are metal elements of 21Ac to 30Zn, 39Y to 48Cd, 57La to 80Hg, and 89Ac or more in the periodic table. Means.
In addition, the typical metal elements of Groups 13 to 16 of the periodic table mean 13Al, 31Ga, 32Ge, 49In, 50Sn, 51Sb, 81Tl, 82Pb, 83Bi, and 84Po in the periodic table.

  The metal compound (1) used in the aqueous solution (B) in the present invention is most preferably a metal oxide. Examples of the metal compound (1) include compounds that can be represented by the general formula AxMyBz. Where A is an alkali metal element, M is a transition metal element of Groups 3 to 12 of the periodic table or a typical metal element of Groups 13 to 16 of the periodic table, and B is from the group consisting of O, CO3 and OH. It is at least one kind of group selected, and x, y, and z are numbers that enable the bonding of A, M, and B. The compound represented by the general formula AxMyBz is preferably a compound that is completely or partially dissolved in water and exhibits basicity. Further, a metal compound in which the metal compound (2) removed by the alkali metal in the metal compound (1) acting as a hydrogen halide remover when it is generated during polymerization hardly or not dissolves in water. (1) is preferable because a metal compound can be complexed with an organic polymer more efficiently.

Among the metal compounds (1) used in the present invention, compounds in which B in the above general formula is O include sodium zincate, sodium aluminate, sodium chromite, sodium ferrite (sodium ferrite), molybdenum Sodium complex oxides such as sodium oxide, sodium stannate, sodium tantalate, sodium titanate, sodium vanadate, sodium tungstate, sodium zirconate, potassium zincate, potassium aluminate, potassium chromite, potassium molybdate , Potassium stannate, potassium manganate, potassium tantalate, potassium ironate, potassium titanate, potassium vanadate, potassium tungstate, potassium goldate, potassium silverate, potassium zirconate, potassium antimonate, etc. Lithium composite oxides such as lithium aluminate, lithium molybdate, lithium stannate, lithium manganate, lithium tantalate, lithium titanate, lithium vanadate, lithium tungstate, and lithium zirconate, as well as rubidium composite oxide and cesium composite An oxide can be suitably used.

Examples of the metal compound (1) in which B in the above general formula includes both groups of CO3 and OH include potassium zinc carbonate, potassium nickel carbonate, potassium zirconium carbonate, potassium potassium carbonate, and potassium tin carbonate. Can do.

Since these metal compounds (1) are dissolved in water and used, they may be hydrates. Moreover, these can be used individually or in combination of 2 or more types.

The aqueous solution (B) in the present invention may contain water glass. By performing the polymerization reaction in the presence of water glass, a complex composed of an organic polymer, a metal compound, and silica can be obtained. The water glass used is represented by a composition formula of A ₂ O.nSiO ₂ such as water glass No. 1, No. 2, No. 3, etc. described in JIS K 1408, where A is an alkali metal element, and the average value of n is The thing of 1.8-4 is mentioned. Similarly to the alkali metal in the metal compound (1), the alkali metal contained in the water glass also acts as a remover for the acid generated during the polymerization, thereby promoting the polymerization reaction.

  The content rate of the metal compound (2) particles in the organic-inorganic composite can be controlled by adjusting the concentration of the metal compound (1) in the aqueous solution (B). The content rate of the metal compound (2) particles contained in the organic-inorganic composite of the present invention is in the range of 20 to 80% by mass with respect to the total mass of the organic-inorganic composite (A). When the content of the metal compound (2) is less than 20% by mass, the function inherent to the metal compound that the metal compound (2) gives to the organic-inorganic composite is insufficient. If the amount exceeds 80% by mass, the function of the organic polymer imparted to the organic-inorganic composite is deteriorated, resulting in poor processability and, when used as paper, the strength of the paper product is reduced. appear.

  The concentration of the metal compound (1) in the aqueous solution (B) is determined to some extent by the monomer concentration in the organic solution (A) and the aqueous solution (B), but maintains a high yield of the organic-inorganic complex, and The range of 1-500 g / L is preferable from the reason which prevents the side reaction with the monomer and water in the organic solution (A) which may be generated by the excessive heat_generation | fever at the time of superposition | polymerization.

  When the concentration of the metal compound (1) in the aqueous solution (B) is lowered for the purpose of producing an organic-inorganic composite with a low content of metal compound, the amount of alkali metal in the synthesis system is insufficient. As a result, hydrogen halide generated during the polycondensation reaction may not be sufficiently neutralized to allow the reaction to proceed. In that case, an acid acceptor such as sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate may be added to the aqueous solution (B), or the acid acceptor solution may be added later to the synthesis system.

  In this invention, it is preferable that the metal compound (1) used for aqueous solution (B) has a basicity higher than the said diamine. More specifically, the pH value due to dissolution of the metal compound (1) in the aqueous solution (B) is preferably higher than the pH value due to dissolution of the diamine in the aqueous solution (B). As described above, the alkali metal in the metal compound (1) has the effect of accelerating the polycondensation reaction by neutralizing the hydrogen halide generated during the polycondensation reaction. If the property is lower than the basicity of the diamine, the side reaction in which the hydrogen halide generated during the polycondensation reaction reacts with the diamine without reacting with the alkali metal in the metal compound (1) occurs preferentially. May be consumed and the yield of the polymer may be greatly reduced. In addition, when this side reaction occurs, the metal compound (1) does not remove the alkali metal in the compound, so it does not convert to a metal compound, but remains in solution in the aqueous solution (B) and is combined with the organic polymer. Therefore, the yield of the metal compound is greatly reduced.

  When the basicity of the metal compound (1) is low, by selecting a diamine having a lower basicity than this, the target polymerization reaction can be performed with a high yield. When the diamine is aliphatic, the basicity tends to decrease as the number of carbon atoms decreases. When the diamine is aromatic, any compound can be suitably used because it is generally low in basicity.

  In the present invention, a known and commonly used surfactant can be used for the purpose of bringing the organic solution (A) and the aqueous solution (B) into good contact.

  The manufacturing apparatus of the organic-inorganic composite in the present invention is not particularly limited as long as the manufacturing apparatus can satisfactorily contact and react the organic solution (A) and the aqueous solution (B). It is also possible with the method. Specific equipment for the continuous type is "Fine Flow Mill FM-15" manufactured by Taihei Koki Co., Ltd., "Spiral Pin Mixer SPM-15" manufactured by the same company, or INDAG Machinenbau Gmb. "Dynamic mixer DLM / S215 type" manufactured by the company and the like can be mentioned. In the case of the batch type, since it is necessary to make good contact between the organic solution and the aqueous solution, a general-purpose stirring device having a propeller blade, a Max blend blade, a Faudler blade, or the like can be used.

  When an aliphatic dicarboxylic acid halide is used as the component in the organic solution (A) and an aliphatic diamine is used as the component in the aqueous solution (B), a strong gel may be formed during the polymerization operation. is there. In that case, it is preferable to use a mixer having a high shearing force for crushing the gel and advancing the reaction. Examples thereof include a blender manufactured by OSTERIZER.

  As for the temperature at which the organic solution (A) and the aqueous solution (B) are subjected to a polycondensation reaction, the reaction proceeds sufficiently in a temperature range of, for example, −10 to 50 ° C. near room temperature. No pressurization or decompression is required. The polymerization reaction is usually completed in a short time of about 10 minutes, although it depends on the monomer used and the reaction apparatus.

In the organic-inorganic composite of the present invention, as an inorganic compound, a transition metal element of Group 3 to Group 12 of the periodic table or a metal oxide, metal hydroxide, and metal carbonate of a typical metal element of Groups 13 to 16 of the periodic table And at least one inorganic compound selected from the group consisting of: As this inorganic compound, a metal oxide is preferable. Examples of the metal oxide include aluminum oxide, tin oxide, zirconium oxide, zinc oxide, manganese oxide, molybdenum oxide, and tungsten oxide. Among these, aluminum oxide is preferable because the average particle diameter of the fine particles is small and the fine dispersibility is good.
On the other hand, the organic polymer of the organic-inorganic composite of the present invention becomes polyamide, polyurethane or polyurea depending on the selection of the monomer used in the organic solution during synthesis. The dispersion shape of the inorganic compound in the organic polymer differs depending on the combination of the metal compound (2), which is an inorganic compound, and the organic polymer. Among these combinations, an organic-inorganic composite in which fine particles of aluminum oxide are finely dispersed in an organic polymer matrix of polyamide is particularly preferable.

The dispersion shape is measured by the following measurement method. First, the organic-inorganic composite is 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. Next, this is made into an ultrathin section having a thickness of 75 nm using a microtome. The obtained slice is observed with a transmission electron microscope “JEM-200CX” manufactured by JEOL Ltd. at a magnification of 100,000. It was observed that the inorganic compounds of the examples of the present invention were finely dispersed in a bright organic polymer as a dark image. The particle diameter of 100 inorganic compound fine particles was measured, and the average value was defined as the average particle diameter of the inorganic compound.

(Aluminum oxide / polyamide)
When the inorganic compound is aluminum oxide and the organic polymer is aliphatic polyamide, a so-called two-dimensional network structure in which plate-like aluminum oxide fine particles having a thickness of about 1 nm and a plane length of about 20 nm are connected in a plane direction. And was dispersed in the polyamide matrix.

(Tin oxide / polyamide)
When the inorganic compound was tin oxide and the organic polymer was aliphatic polyamide, it was observed that spherical tin oxide fine particles having a diameter of about 100 to 1000 nm were dispersed in the polyamide matrix in an independent state.

(Aluminum oxide / polyurea)
When the inorganic compound is aluminum oxide and the organic polymer is aliphatic polyurea, spherical aluminum oxide fine particles having a diameter of about 10 nm have a so-called three-dimensional network dimensional network structure in which the particles are connected in all directions, Dispersion in the polyurea matrix was observed.

(Tin oxide / polyurea)
When the inorganic compound is tin oxide and the organic polymer is aliphatic polyurea, it is observed that spherical metal oxide fine particles having a diameter of about 100 to 1000 nm are dispersed in the polyurea matrix in an independent state. It was done.

(Aluminum oxide / Polyurethane)
When the inorganic compound is aluminum oxide and the organic polymer is aliphatic polyurethane, a so-called three-dimensional network structure in which spherical aluminum oxide fine particles having a diameter of about 10 nm are connected in all directions is used in the polyurethane matrix. It was observed that it was dispersed.

(Tin oxide / polyurethane)
When the inorganic compound was tin oxide and the organic polymer was aliphatic polyurethane, it was observed that spherical metal oxide fine particles having a diameter of about 100 to 1000 nm were dispersed in the polyurethane matrix in an independent state. .

(Average particle size)
The average particle diameter of the fine particles of the inorganic compound in the organic-inorganic composite of the present invention is preferably 500 nm or less, more preferably 150 nm or less, and further preferably 100 nm or less because the composite effect is further obtained.

Hereinafter, the present invention will be described more specifically with reference to examples. Unless otherwise specified, “part” means “part by mass”.
Example 1 (Aluminum oxide (alumina) / polyamide composite)
Ion-exchanged water (81.1 parts), 1,6-diaminohexane (1.58 parts), sodium aluminate.n hydrate (a mixture of NaAlO ₂ .nH ₂ O and Na ₃ AlO ₃ .nH ₂ O, Al / (NaOH = 0.8) 2.96 parts was added and stirred at room temperature for 15 minutes to obtain a homogeneous transparent aqueous solution (B). This aqueous solution was charged into a blender bottle manufactured by Osterizer at room temperature, and an organic solution (A) in which 2.49 parts of adipoyl chloride was dissolved in 44.4 parts of toluene was stirred for 20 seconds while stirring at 10,000 rpm. It was dripped over. The generated gel was crushed with a spatula and further stirred at 10,000 rpm for 40 seconds. The liquid in which the pulp-like product obtained by this operation was dispersed was filtered under reduced pressure on a filter paper having a mesh size of 4 μm using a Nutsche having a diameter of 90 mm. The product on Nutsche was dispersed in 100 parts of methanol, stirred for 30 minutes with a stirrer, and filtered under reduced pressure for washing treatment. Subsequently, the same washing operation was performed using 100 parts of distilled water to obtain a white organic-inorganic composite wet cake.

  200 g of a dispersion obtained by dispersing the obtained organic-inorganic composite in distilled water at a concentration of 0.2 g / dL was filtered under reduced pressure on a filter paper having a mesh size of 4 μm using a Nutsche having a diameter of 55 mm. The obtained cake was hot-pressed at 170 ° C. and 5 MPa / cm 2 for 2 minutes to prepare a nonwoven fabric.

(Example 2) (tin oxide / polyamide composite)
1.20 parts of 1,4-diaminobutane and 3.96 parts of sodium stannate trihydrate (Na ₂ SnO ₃ .3H ₂ O) are placed in 81.8 parts of ion-exchanged water as an aqueous solution (B) at 25 ° C. Was stirred for 15 minutes to prepare a homogeneous transparent aqueous solution. As an organic solution (A), an organic solution in which 3.26 parts of sebacoyl chloride was dissolved in 44.4 parts of toluene was prepared. A white organic-inorganic composite was obtained in the same manner as described in Example 1 except that these raw material solutions were used. Moreover, the nonwoven fabric was created by the method similar to the method described in Example 1. FIG. The obtained non-woven fabric was rich in flexibility.

Example 3 (Zirconium oxide / polyamide composite)
As an aqueous solution (B), 1.58 parts of 1,6-diaminohexane and 3.79 parts of potassium zirconium carbonate (K ₂ [Zr (OH) ₂ (CO ₃ ) ₂ ]) are added to 81.1 parts of ion-exchanged water and stirred. A white organic-inorganic composite was obtained in the same manner as in the method described in Example 1 except that the homogeneous solution thus obtained was used. Moreover, the nonwoven fabric was created by the method similar to the method described in Example 1. FIG. The obtained non-woven fabric was rich in flexibility.

(Comparative Example 1) (Aluminum oxide / polyamide composite prepared by melt-kneading method)
As a polymer, 80.0 parts of nylon 66 pellets and 20.0 parts of aluminum oxide powder having an average particle size of 100 nm are melt-kneaded at 270 ° C. in a small twin screw extruder MP2015 made by Tsubako, thereby forming a pellet-like organic-inorganic composite. Got the body. The raw material charging operation prior to the kneading operation is very difficult because powder scattering due to the extremely small particle size of aluminum oxide is likely to occur.

  The organic inorganic composites obtained in Examples 1 to 3 and Comparative Example 1 and the nonwoven fabric were measured or tested for the following items, and the results obtained are shown in Table 1.

(1) Measuring method of inorganic compound content rate (ash content) The measuring method of the content rate of the inorganic compound contained in the organic-inorganic composite is as follows.
The organic-inorganic composite was thoroughly dried (composite mass), calcined in air at 700 ° C. for 3 hours to completely burn off the organic polymer component, the mass after firing was measured, and the ash content (= inorganic) Compound mass). The inorganic compound content was calculated from the following formula.
Inorganic compound content (mass%) = (ash content / composite mass) × 100

(2) Verification of metal compound species in organic-inorganic composite The nonwoven fabrics of Examples 1 to 3 were cut into 3 cm squares, and this was set in a measurement holder having a diameter of 20 mm to obtain 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 obtained results of total elemental analysis, the sample data of the sample for measurement (the data given is sample shape: film, compound type: oxide, correction component: cellulose, mass value per area of the measured sample) Presence of elements in the complex by the FP method (Fundamental Parameter method: A method in which sample uniformity and surface smoothness are assumed and correction is performed using constants in the device and the components are quantified). The percentage was calculated. It was shown that the target metal compound was present in a large amount in the samples obtained in any of the examples. In addition, the content rate of the target metal compound measured by this method agreed with the calculation result of the inorganic compound content rate obtained in (1) within an error range of 0.5% by mass.

(3) Calculation of alkali metal removal rate Moreover, the alkali metal removal rate (%) calculated by the following formula using the amount of alkali metal in the nonwoven fabric measured in (2) and the alkali metal content at the time of raw material charging = (=) 1-R) × 100
R = alkali metal content in nonwoven fabric (%) / alkali metal content at preparation (%)

(4) Particle size measurement of inorganic compound 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 section having a thickness of 75 nm using a microtome. The obtained section was observed with a transmission electron microscope “JEM-200CX” manufactured by JEOL Ltd. at a magnification of 100,000. It was observed that the inorganic compound was finely dispersed in a bright organic polymer as a dark image. The particle size of 100 inorganic compound particles was measured, and the average value was defined as the inorganic compound average particle size. FIG. 1 shows a transmission electron micrograph of the alumina / polyamide composite obtained in Example 1.

(5) Calculation of yield of organic-inorganic composite The yield (%) of the organic-inorganic composite was calculated by the following formula. However, the mass actually generated was defined as the total mass of the organic-inorganic composite.
Yield (%) = [total mass of formed organic / inorganic composite / (metal compound mass in theoretical yield + organic polymer mass in theoretical yield)] × 100

  As shown in Table 1, in Comparative Example 1, although the aluminum oxide powder having an average particle diameter of 100 nm was used as the inorganic compound, the inorganic compound aggregated in the kneading step, and the resulting organic-inorganic composite The average particle diameter of the fine particles of the inorganic compound (aluminum oxide) was 1800 nm (1.8 μm), and it was not possible to perform nanometer order composite.

On the other hand, as shown in Examples 1 to 3, in the organic-inorganic composite obtained by the present invention, as a compound from which the alkali metal constituting the metal compound (1) was almost completely removed, It was revealed that they were uniformly compounded. Further, the particle size of the inorganic compound fine particles was on the order of nanometers, and the inorganic compound content was 40% by mass or more. Moreover, the organic-inorganic composite having the above characteristics could be obtained by a short operation under normal temperature and pressure.

In the organic-inorganic composite of the present invention, the inorganic compound is finely dispersed in the nanometer order in the organic polymer matrix. Moreover, there is also much content of an inorganic compound. Therefore, the moldability and flexibility of organic materials and the functions of various metal compounds (for example, hardness, catalytic ability, insulation, semiconductivity, electronic conductivity, ionic conductivity, high specific surface area, high heat resistance, wear resistance) Or an organic-inorganic composite having both dimensional stability against temperature change and moisture absorption). Therefore, the organic-inorganic composite of the present invention is extremely useful industrially.

2 is a transmission electron micrograph of the alumina / polyamide composite obtained in Example 1. FIG.

Claims (8)

At least one organic polymer selected from the group consisting of polyamide, polyurethane and polyurea;
From metal oxides, metal hydroxides and metal carbonates of transition metal elements of Group 3 to Group 12 of the periodic table or typical metal elements of Groups 13 to 16 of the periodic table finely dispersed in the matrix of the organic polymer Fine particles of at least one inorganic compound selected from the group consisting of:
Wherein the average particle diameter of the fine particles of the inorganic compound is 1 μm or less, and the content of the fine inorganic compound particles in 100% by mass of the composite is 20 to 80% by mass. An organic-inorganic composite. The organic-inorganic composite according to claim 1, wherein the transition metal element of Group 3 to Group 12 of the periodic table or the typical metal element of Groups 13 to 16 of the periodic table is aluminum, zirconium, zinc, tin, and titanium. The organic-inorganic composite according to claim 1, wherein the inorganic compound is a metal oxide. The organic-inorganic composite according to claim 1, wherein the metal oxide is at least one inorganic compound selected from the group consisting of aluminum oxide, zirconium oxide, zinc oxide, tin oxide, and titanium oxide. The organic-inorganic composite according to claim 1, wherein the organic-inorganic composite has a pulp shape having a fiber diameter of 20 μm or less and an aspect ratio of 10 or more. 2. The organic-inorganic composite according to claim 1, wherein an average particle size of the inorganic compound fine particles is 100 nm or less. The organic-inorganic composite according to claim 1, wherein the organic-inorganic composite further contains silica. An organic solution (A) in which at least one compound selected from the group consisting of a dicarboxylic acid halide, a dichloroformate compound, and a phosgene compound is dissolved in an organic solvent;
From the group consisting of metal oxides, metal hydroxides and metal carbonates of at least one alkali metal element and a transition metal element of Group 3 to Group 12 of the periodic table or a typical metal element of Groups 13 to 16 of the periodic table The method for producing an organic-inorganic composite according to claim 1, wherein the at least one metal compound selected and a basic aqueous solution (B) containing diamine are mixed and stirred to react.

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