JP2009227771A - Method for producing organic-inorganic composite - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for easily producing an organic-inorganic composite wherein an inorganic component is dispersed. <P>SOLUTION: In the method for producing an organic-inorganic composite, an organic solvent solution (1) containing at least one kind of a monomer (a) selected from a group consisting of a dicarboxylic acid halide, a dichloroformate compound, and a phosgene compound and a diamine (b) is mixed with an aqueous solution (2) comprising a metal compound (c-1) selected from a group consisting of a metal oxide, a metal hydroxide, and a metal carboxide and containing two or more metal elements including at least one alkali metal and an alkali silicate (c-2) after partially reacting the monomer (a) with the diamine (b) by heating the organic solvent solution (1), and then, the organic solvent solution (1) and the aqueous solution (2) are kept compatible partially or made coexist in the separated state for further reacting the monomer (a) with the diamine (b), and simultaneously, precipitating the inorganic component. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing an organic-inorganic composite using polyamide, polyurea, and polyurethane as a matrix polymer.

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

An example is disclosed in which an organic-inorganic composite containing nano-sized inorganic fine particles at a high filling rate using a polymer such as polyamide, polyurea, or polyurethane as a matrix polymer is disclosed. For example, Patent Document 1 describes a method for producing an organic-inorganic composite of silica and polyamide by a method in which an aqueous solution obtained by dissolving diamine and alkali silicate in water is reacted with a dicarboxylic acid halide dissolved in an organic solvent. Patent Document 2 discloses a metal obtained by a method in which an aqueous solution in which a diamine and an alkali metal-containing composite oxide are dissolved in water is reacted with a dicarboxylic acid halide, a dichloroformate compound, or a phosgene compound dissolved in an organic solvent. A method for producing an organic-inorganic composite such as an oxide and polyamide, polyurea, or polyurethane is described.
These methods are all methods in which an aqueous solution of diamine and an organic solution such as dicarboxylic acid halide are reacted by an interfacial polycondensation method, and therefore, the diamine as a raw material must be completely dissolved in water.

  For example, paragraph 0022 of Patent Document 2 describes aromatic diamines such as phenylenediamine and diaminonaphthalene as examples of diamines. However, since aromatic diamines have many compounds with extremely low solubility in water, the above method cannot sufficiently supply the monomers necessary for polymer polymerization into the synthesis system, and the reaction is expected because the monomer concentration in water is low. There was a problem that the molecular weight of the organic component of the obtained organic-inorganic composite did not proceed and the molecular weight was very low. Polyamides made from diamines having a plurality of aromatic ring sites are polymers with high heat resistance and high demand as engineering plastics, but organic-inorganic composites using such polymers as a matrix are those desired in the above method. Can't get.

  Moreover, the said method is reaction which starts a polymer synthesis | combination and inorganic precipitation by making a polymer raw material exist separately in aqueous solution and an organic solution, and making both solutions contact. Therefore, when the polymer synthesis reaction rate is close to the inorganic precipitation rate, the inorganic component is dispersed with a fine particle size in the polymer, but when both reaction rates are different, solidification of the component with a fast reaction rate is achieved. As a result of the progress of the above, there was a problem that the composite with a fine particle size was not successful and the deposited inorganic material was coarsened. In particular, when the inorganic precipitation rate is too high, or the polymer synthesis rate is too low, this problem becomes significant. However, in the above-described method, there is no effective method for controlling these reaction rates other than the successful combination of the inorganic material and the polymer raw material to be used, and the composition of the obtained organic-inorganic composite is limited.

On the other hand, there is also known a technique in which polyamide is melted and kneaded at a melting point or higher and inorganic particles are melted and kneaded with an extruder or the like. However, the method of melt-kneading nano-sized inorganic particles causes secondary agglomeration during kneading, and in the case of aromatic polyamide, the melting point is 350 ° C. or higher, and the kneading temperature is very high. However, even if melt kneading is possible, there is a problem that a large amount of energy is required for production.
JP-A-10-176106 JP 2005-036211 A

  The problem to be solved by the present invention is to combine an organic-inorganic composite in which a polymer such as polyamide, polyurea, or polyurethane is used as a matrix and an inorganic component is dispersed with a particle diameter of preferably 100 nm or less, and a combination of monomer raw materials and inorganic raw materials. It is providing the method of obtaining easily without limiting.

The inventor makes a dicarboxylic acid halide or the like and a diamine coexist in an organic solvent in a state in which each of them is unreacted or hardly undergoes reaction to form a uniform organic solvent solution, and further heats the organic solvent solution. And 2) containing at least one alkali metal selected from the group consisting of metal oxides, metal hydroxides and metal carbonates after proceeding to some extent by the reaction of dicarboxylic acid halide and the like with diamine to oligomerize (preliminary polymerization). It has been found that the above problem can be solved by mixing with a metal compound having two or more metal elements or an aqueous solution containing an alkali silicate.
By pre-oligomerizing dicarboxylic acid halide and diamine with diamine in advance, it is possible to prevent the inorganic precipitation reaction from proceeding too much, and then to make both reaction rates after contacting both solutions (appearance) substantially constant, respectively. It is possible to approach the reaction end time of. In addition, the oligomer chain can prevent coarse precipitation of inorganic components.

  That is, the present invention relates to an organic solvent solution (1) containing at least one monomer (a) and diamine (b) selected from the group consisting of a dicarboxylic acid halide, a dichloroformate compound, and a phosgene compound, and a metal oxide. An aqueous solution containing a metal compound (c-1) having two or more metal elements containing at least one alkali metal selected from the group consisting of a product, a metal hydroxide and a metal carbonate, and an alkali silicate (c-2) (2) is mixed after the monomer (a) and the diamine (b) are partially reacted by heating the organic solvent solution (1), and the organic solvent solution (1) and the The aqueous solution (2) is allowed to coexist in a state where it is at least partially compatible or separated, and the reaction between the monomer (a) and the diamine (b) is further advanced, and at the same time, the inorganic component is precipitated. Provided is a method for producing an organic-inorganic composite.

According to the present invention, an organic-inorganic composite in which a polymer having high heat resistance such as polyamide, polyurea, polyurethane and the like using aromatic diamine as a raw material is used as a matrix polymer, and inorganic components are dispersed in the matrix polymer with a minute particle size of 100 nm or less. The body can be easily obtained.
In the present invention, the combination of monomer raw materials and inorganic raw materials is not limited, so that various combinations of organic-inorganic composites can be obtained. In addition, the production method of the present invention can be performed in one step in a short time at room temperature and normal pressure using a general-purpose stirrer.
Furthermore, the production method of the present invention can easily obtain an organic-inorganic composite using an aromatic diamine hardly soluble in water as a raw material.

(Organic solvent solution (1))
The organic solvent solution (1) used in the present invention contains at least one monomer (a) selected from the group consisting of a dicarboxylic acid halide, a dichloroformate compound, and a phosgene compound, a diamine, and an organic solvent.

(Monomer (a) Dicarboxylic acid halide)
Examples of the dicarboxylic acid halide include an acid halide of an aliphatic dicarboxylic acid such as succinic acid, adipic acid, azelaic acid, and sebacic acid, an acid halide of an aromatic dicarboxylic acid such as isophthalic acid and terephthalic acid, or an aromatic ring of these aromatic rings. Dicarboxylic acids composed of a plurality of aromatic rings such as acid halides of aromatic dicarboxylic acids in which hydrogen is substituted with halogen atoms, nitro groups, alkyl groups, 2,6-naphthalenedicarboxylic acid dichlorides, 1,5-naphthalenedicarboxylic acid dichlorides, etc. Examples of the acid halides may be used singly or in combination of two or more. Of these, halides of aromatic dicarboxylic acids are particularly preferably used because they have a lower reactivity with diamines than halides of aliphatic dicarboxylic acids and can be easily retained in a state dissolved in an organic solvent together with diamines.

(Monomer (a) Dichloroformate compound)
Examples of the dichloroformate compound include 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, and the like. Aliphatic diols, resorcin (1,3-dihydroxybenzene), hydroquinone (1,4-dihydroxybenzene), 1,6-dihydroxynaphthalene, having two hydroxyl groups in one or more aromatic rings, , 2'-biphenol, bisphenol S, bisphenol A, tetramethylbiphenol and the like, all hydroxyl groups of divalent phenols are chlorogenated by phosgenation treatment. . These can be used alone or in combination of two or more. Among them, a compound having an aromatic ring is particularly preferably used because it has a lower reactivity with a diamine than an aliphatic compound and can be easily retained in a state dissolved in an organic solvent together with the diamine.

(Monomer (a) Phosgene compound)
Examples of the phosgene compound include phosgene, diphosgene and triphosgene. These can be used alone or in combination of two or more. Further, the dicarboxylic acid halide or the dichloroformate compound may be used in combination.

  When a dicarboxylic acid halide is used as the monomer (a), the matrix polymer of the obtained organic-inorganic composite is polyamide. When a dichloroformate compound is used, the resulting organic / inorganic composite matrix polymer is polyurethane. When a phosgene compound is used, the resulting organic / inorganic composite matrix polymer is polyurea.

(Diamine (b))
The diamine (b) used in the present invention is not particularly limited as long as it can be dissolved in a later-described organic solvent in a certain amount or more, but an aromatic diamine is preferable because the effects of the present invention can be exhibited most. Specifically, diamine having one aromatic ring such as metaphenylenediamine, paraphenylenediamine, metaxylylenediamine, paraxylylenediamine, chlorophenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, and toluylene diene Amine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 4,4'-thiodianiline, 4,4'-diaminobenzanilide, 1,5- Examples thereof include diamines having a plurality of aromatic rings such as naphthylenediamine and 1,6-naphthylenediamine. Many of these aromatic diamine monomers are excellent in basic properties such as high heat resistance, and because they have low solubility in water, the method shown in the above-mentioned patent document can provide a desired polymer. Although difficult, the method of the present application can be easily polymerized. In particular, in the present invention, diamine (b) having a solubility in water at 20 ° C. of 5% by mass or less is preferable because it can be efficiently reacted.

  Moreover, it is possible to use not only the illustrated diamine but also any diamine that can stably coexist with the monomer (a) in an organic solvent. Examples include side chain aliphatic diamines and alicyclic diamines. Examples of the side chain aliphatic diamine include 1,2-diaminopropane, 2-methyl-1,5-diaminopentane, and trimethylhexamethylenediamine. Examples of the alicyclic diamine include 1,3-cyclohexane diamine, 1,4-cyclohexane diamine, isophorone diamine, and 4,4′-diaminodicyclohexane methane. On the other hand, a highly reactive diamine such as a linear aliphatic diamine may not be able to stably coexist with the monomer (a) in an organic solvent.

  In the present invention, the acid dissociation constant (pKa) of the first and second dissociation stages of diamine can be used as an index of diamine (b) that can be particularly preferably used. If the pKa of the diamine is high, the basicity in the solution is high, so that the diamine itself acts as an acid remover and the organic solvent solution (1) alone may cause a polymer synthesis reaction. Therefore, the pKa of diamine (b) is 7 or less, particularly preferably 5 or less, in both the first and second dissociation stages. The dissociation constants of almost all wholly aromatic diamines are within this range.

(Organic solvent)
In the present invention, matrix polymers such as polyamide, polyurethane, polyurea, and the like are precipitated during the synthesis reaction, so that inorganic fine particles are achieved by maintaining the inorganic components that are simultaneously precipitated at the nano particle size. Therefore, it is preferable that the organic solvent used in the present invention can be dissolved without reacting the monomer (a) and the diamine (b), and at the same time, has low solubility in the synthesized polymer. On the other hand, polyamides, polyurethanes, and polyureas vary greatly in solubility in organic solvents depending on their structures, and therefore it is preferable to select them appropriately in consideration of the solubility of the resulting polymer. Further, since it is necessary to react a certain amount of the monomer (a) and the diamine (b) in a situation where there is no material having a function as a deoxidizer such as alkali silicate (c-2), the polymerization reaction may be inhibited. A solvent other than the protic solvent is preferred. Of these, a nitrogen-containing acid-accepting aprotic solvent is preferred because it allows a certain amount of prepolymerization to proceed. Specific examples of the organic solvent used in the present invention include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as n-hexane, tetrahydrofuran, dimethyl ether, diethyl ether, and dibutyl ether. Ethers such as anisole, ketones such as acetone, 2-butanone and cyclohexanone, alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate, halogenated hydrocarbons such as chloroform and methylene chloride, n- Examples thereof include nitrogen-containing organic solvents such as methyl pyrrolidone, NN-dimethylacetamide, dimethylformamide, propylene carbonate, dimethyl sulfoxide and the like. A plurality of these may be used in combination in order to dissolve the monomer (a) and the diamine (b) satisfactorily.

(Monomer concentration)
The monomer concentration of the monomer (a) and the diamine (b) in the organic solvent solution (1) 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, A concentration range of 0.01 to 3 mol / L, particularly 0.05 to 1 mol / L is preferred.

(Preliminary polymerization conditions)
The organic solvent solution (1) is preferably cooled from the time when the monomer (a) or diamine (b) is blended. The cooling temperature is preferably room temperature or lower, and preferably about −30 to 15 ° C. Depending on the type and combination of the monomers, heat may be generated due to oligomer synthesis simultaneously with the mixing of the monomer (a) and the diamine (b). When temperature control is not performed, once the temperature in the synthesis system rises due to heat generation, the reaction cannot be controlled and the molecular weight may increase at once. Therefore, cooling is preferably performed to prevent such a state.

The cooled organic solvent solution (1) is slowly heated, and the monomer (a) and the diamine (b) are partially reacted (hereinafter referred to as prepolymerization reaction) to be oligomerized. The rate of temperature increase at this time is not particularly limited, but since too rapid heating promotes the reaction rate more than necessary, specifically 1 to 20 ° C./min is preferable. The heating (reaction temperature) is preferably in the range of 25-60 ° C. If the heating is less than 25 ° C., the polymerization reaction does not proceed sufficiently, so that it does not become an oligomer and the effects of the present invention may be difficult to achieve. On the other hand, if the heating exceeds 60 ° C., the polymerization reaction proceeds too much to become a polymer, and it may be difficult to complex the inorganic component in the atomized state in the subsequent inorganic precipitation reaction. The warming holding time at this time is preferably 30 minutes to 3 hours in order to balance the prepolymerization state and the production rate, but these warming temperatures and warming holding times are the types of monomers used. Or may be adjusted as appropriate depending on the combination.
On the other hand, the hydrogen halide generated by the prepolymerization reaction is accumulated in the organic solvent solution (1) and has an effect of preventing polymerization by further polymerization, so that it can be maintained in an oligomer state.

In addition, oligomerization is also possible by a method in which a material used as a deoxidizer for polycondensation in an organic solvent is added to the solvent solution (1) in a smaller amount than that required for polymer synthesis. Since a polycondensation reaction occurs depending on the amount of the deoxidizer added, it is possible to adjust the molecule. Deoxidizers include basic inorganic compounds such as calcium chloride, magnesium chloride, calcium hydroxide, magnesium hydroxide, lithium hydroxide, sodium hydroxide and potassium hydroxide, and amines such as trimethylamine, triethylamine, tributylamine and pyridine. Compounds.
The addition amount of the deoxidizer depends on the monomer species used as a raw material, but generally it is preferably adjusted appropriately within a range of 1 to 30% of the amount required for normal polymer synthesis. In addition, a deoxidizer may be used in combination with the prepolymerization method by heating.

Moreover, as a standard of molecular weight, it is preferable that the average value of the number of repeating units n is oligomerized to about 1 to 15 in terms of the degree of polymerization.
When n is less than 1, since the prepolymerization reaction is insufficient, the effect of atomizing the inorganic particles may be insufficient. On the other hand, when n is larger than 15, the polymer is likely to be precipitated in the organic solvent (1), and the inorganic particles may not be dispersed with a fine particle size in the subsequent inorganic precipitation reaction. The molecular weight range varies depending on the type of monomer used, but is preferably in the range of 400 to 5000 in terms of number average molecular weight.

(Aqueous solution (2))
The raw material of the inorganic component of the organic-inorganic composite in the present invention is an alkali metal salt of an inorganic compound. Specifically, a metal compound (c-1) having two or more metal elements containing at least one alkali metal selected from the group consisting of metal oxide, metal hydroxide and metal carbonate (hereinafter referred to as metal compound ( c-1)) or alkali silicate (c-2) is preferred because it is readily available and inexpensive. When the metal compound (c-1) is used as a raw material, a metal compound having a metal element other than an alkali metal is precipitated. When an alkali silicate (c-2) is used as a raw material, silica (silicon oxide) is precipitated. (Hereinafter, “metal compound (c-1) or alkali silicate (c-2)” may be abbreviated as “compound (c)”).

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

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

(Solvent of aqueous solution (2))
The compound (c) is dissolved in water and used as an aqueous solution (2). When the reaction with the organic solvent solution is carried out in a compatible state, a polar organic solvent such as acetone, tetrahydrofuran or N-methylpyrrolidone is mixed up to about 30% by mass of the aqueous solution (2), Solubility may be adjusted. The addition of the polar organic solvent is also effective for preventing the aqueous solution (2) from solidifying. 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. Furthermore, polymer synthesis may be promoted and clay components may be combined by partially mixing clay minerals (alkali-containing clay, etc.) that exhibit alkalinity when swollen and dispersed in water.

  Plural inorganic components (in the present invention, “inorganic component” refers to an inorganic compound not containing an alkali metal deposited by the method for producing an organic-inorganic composite of the present invention. Further, the compound (c) is obtained as a raw material. Inorganic component is referred to as “inorganic component (c)”) in the organic-inorganic composite, the metal compound (c-1) or the alkali silicate (c-2) is used in combination. Also good. However, depending on the combination, the inorganic component (c) may gel or precipitate in the aqueous solution (2), and the inorganic component (c) may not be able to be combined in a fine particle state. Need attention.

(Inorganic compound and other components, metal compound (c-3))
By adding the metal compound (c-3) that dissolves in the basic aqueous solution and precipitates in the neutral aqueous solution to the aqueous solution (2), the inorganic component of the organic-inorganic composite can be diversified and further functions can be imparted. There is a way. 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 inorganic component to be precipitated is only the inorganic component (c), and the metal compound (c-3) remains in a dissolved state. As the reaction proceeds and the aqueous solution approaches neutrality, the metal compound (c-3) precipitates. Thus, unlike the compound (c), the metal compound (c-3) is compounded with the composition as it is. Therefore, the obtained organic-inorganic composite has a structure in which the inorganic component (c) is uniformly dispersed in the polymer matrix and the metal compound (c-3) is supported on the inorganic main component on the outermost surface. .

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.

(Production method)
The method for producing an organic-inorganic composite of the present invention comprises an organic solvent solution (1) containing the aforementioned monomer (a) and diamine (b) and prepolymerized part thereof, and the aforementioned compound (c). Maintaining at least a part of the aqueous solution (2) to be contained or coexisting it in a separated state to react the monomer (a) and the diamine (b) and at the same time precipitate the inorganic component. It is a feature. This makes it possible to bring the reaction end points closer to each other by making the polymer polymerization reaction rate of the monomer (a) and the diamine (b) and the precipitation rate of the inorganic component almost constant, and both components are good. It is possible to synthesize organic-inorganic composites that are dispersed and have a smaller inorganic particle size.
The production method of the present invention is particularly effective when obtaining an organic-inorganic composite in which a polymer species having low reactivity and an inorganic raw material having a fast inorganic precipitation reaction are combined.
Examples of the polymer species having low reactivity include wholly aromatic dicarboxylic acid halides, wholly aromatic dichloroformate compounds, and phosgene compounds. In addition, examples of the inorganic material having a fast precipitation reaction include materials having a high sol-gel reaction rate such as tin oxide and zirconium oxide.
Polycondensation reaction involving deoxidation (dehydrohalogenation) between the monomer (a) and the diamine (b) by the alkali metal compound contained in the metal compound (c-1) and the alkali silicate (c-2) Is promoted to produce polyamide, polyurethane and polyurea polymers.

  On the other hand, the hydrogen halide generated by the polycondensation of the polymer (including the hydrogen halide generated by the prepolymerization of the monomer (a) and the diamine (b) described above) reacts with the alkali metal compound in the inorganic raw material. Then, an alkali halide such as NaCl is generated. Thus, the polymerization reaction proceeds one after another without accumulating hydrogen halide in the synthesis system, and the organic component can be polymerized. On the other hand, the generated alkali halide is discharged out of the synthesis system by dissolving in water in the synthesis system or in the washing process.

(Precipitation reaction of inorganic components)
On the other hand, the metal compound (c-1) and the alkali silicate (c-2) from which the alkali metal has been released are remarkably reduced in solubility in water and organic solvents, and thus precipitate as inorganic components. For example, when sodium silicate is used, -Si-ONa becomes a silanol group (-Si-OH) during the deoxidation reaction. A plurality of the generated silanol groups associate to cause a dehydration polycondensation reaction to form a (—Si—O—Si—) bond. Silica is solidified and precipitated by this sol-gel reaction. Tin oxide is produced when sodium stannate is used as the metal compound (c-1), and aluminum oxide is produced when sodium aluminate is used.

  The synthesis reaction of the polymer and the precipitation reaction of the inorganic compound each have an action of promoting the other reaction. Therefore, it is considered that only one of the reactions does not occur unilaterally and proceeds almost simultaneously. Since the inorganic compound is simultaneously deposited while the polymer is synthesized, a composite in which the fine inorganic compound is uniformly dispersed in the polymer can be obtained by a simple synthesis operation.

(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 is preferably in the vicinity of the temperature after heating the organic solvent solution (1), and specifically in the range of 25 ° C to 60 ° C. Further, pressurization and decompression are not particularly required. The organic-inorganic composite synthesis reaction is usually completed in a short time of 60 minutes or less, depending on the type of monomer used, the reaction apparatus, and the scale.

(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). Although it is possible, the batch method is more preferable from the viewpoint that the contact reaction time can be adjusted and the temperature control is easy. 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 satisfactorily contact 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 Foudra blade.

(Inorganic component of organic-inorganic composite)
The inorganic component of the organic-inorganic composite obtained by the production method of the present invention is appropriately selected according to the purpose because the shape and properties obtained by the metal compound (c-1) and alkali silicate (c-2) used are different. do it. For example, when the metal compound (c-1) is used, the inorganic components are obtained as metal oxides such as aluminum oxide (alumina), tin oxide, zinc oxide, and zirconium oxide. Certain alkali aluminates, alkali stannates, alkali zincates and alkali alkali carbonates are inexpensive. When alkali silicate (c-2) is used, silica is obtained as an inorganic component, and an organic-inorganic composite having a small inorganic particle size is obtained. The production method of the present invention is also characterized in that the obtained inorganic component has a small particle size, and an organic-inorganic composite having an average particle size of 100 nm or less can be obtained.

(Content of inorganic main component based on 100% by mass of organic-inorganic composite)
The inorganic main component derived from the metal compound (c-1) or alkali silicate (c-2) in the organic-inorganic composite obtained in the present invention is the heat resistance, wear resistance, etc., surface hardness, heat dissipation, etc. possessed by the inorganic material. A characteristic such as a characteristic is given. Further, when the metal compound (c-3) is used in combination, it also has a role of supporting the metal compound (c-3).
Therefore, the content of the inorganic main component with respect to 100% by mass of the total amount of the organic-inorganic composite is preferably a certain value or more, preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and most preferably. Is 30 to 60% by mass. If the content is too high, sheeting, processability to laminates, etc., or kneadability to other resins may be impaired.

  On the other hand, when the metal compound (c-1) or the alkali silicate (c-2) and the metal compound (c-3) are used in combination, the metal compound (c-3) is obtained from a reaction mechanism of synthesis. It exists in a supportive manner on the inorganic main component on the outermost surface of the organic-inorganic composite. Therefore, the amount of the metal compound (c-3) is practically less than the inorganic main component. Specifically, it is preferable that a maximum amount of about 15% by mass is supported with respect to 100% by mass of the total amount of the organic-inorganic composite. Since the metal compound (c-3) is supported in a nano size, the supporting effect is high. Depending on the application, the metal compound (c-3) functions if supported by 0.01% by mass or more. A particularly preferable range is 0.1 mass% to 10 mass%. The amount of the metal compound (c-3) supported is governed by the amount dissolved in the aqueous solution (2). For example, in order to increase the loading amount, a metal having high solubility in water is selected as the metal compound (c-3) to be used, and a large amount is dissolved in the aqueous solution (2) to synthesize an organic-inorganic composite. Just do it.

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

Examples 1 to 7 show a method for producing an organic-inorganic composite containing an inorganic component monocomponent system.
Example 1
(Synthesis Method of Polyamide / Aluminum Oxide Composite-1)
Using 19 g of NN-dimethylacetamide as the organic solvent, 2.84 g of terephthalic acid chloride as the dicarboxylic acid halide of monomer (a) was placed in this organic solvent in a 50 cm ³ three-necked flask and dissolved by stirring with an anchor blade at room temperature in a nitrogen stream. After that, the outer periphery of the flask was cooled to 0 ° C. with ice water. Next, an organic solvent in which 3.133 g of 4,4-thiodianiline as a diamine (b) was dissolved in 19 g of NN-dimethylacetamide preliminarily cooled to 0 ° C. was added to the three-necked flask. In the organic solvent solution (1-1), dicarboxylic acid halide and diamine were dissolved at the same time, but a phenomenon showing polymerization of precipitates and the like was not observed.
While stirring the organic solvent solution (1-1) at a heating rate of 2 ° C./min up to 30 ° C., stirring was performed for 1 hour at a rotational speed of 150 rpm while maintaining this temperature state. No precipitate that appeared to be a reaction product was generated. In this state, 0.1 g of liquid was sampled, and molecular weight distribution was measured by the method described later (Measurement 1). As a result, the organic solvent solution (1-1) was an oligomer having a peak at a molecular weight of about 1500 (recurring unit conversion). N = about 4). Next, 2.504 g of powdered sodium aluminate P-100 manufactured by Asada Chemical Industry Co., Ltd. was added as a metal compound (c-1) to 35 g of ion-exchanged water, and stirred at room temperature for 10 minutes to obtain a transparent light yellow aqueous solution. (2-1) was obtained.
This aqueous solution (2-1) was dropped into the three-necked flask over 10 seconds. As the aqueous solution (2-1) was added dropwise, a pale yellow precipitate gradually precipitated. When the dropping of the aqueous solution was completed, the stirring rotation speed was increased to 200 rpm, and stirring was continued for 30 minutes while maintaining the temperature control to obtain a slurry containing a powdery 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 paste-like 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 distilled water, washed with water by stirring for 30 minutes at room temperature, and the dispersion was filtered by the same method as above to obtain a water-containing organic-inorganic composite. This was dried with hot air at 150 ° C. for 5 hours to obtain a dry organic-inorganic composite.

(Example 2)
(Synthesis Method of Polyamide / Aluminum Oxide Composite-2)
19 g of N-methylpyrrolidone as an organic solvent and 2.84 g of terephthalic acid chloride as a monomer (a) in this organic solvent were placed in a 50 cm ³ three-necked flask and dissolved by stirring at room temperature in a nitrogen stream. Cooled to. Next, an organic solvent in which 1.514 g of paraphenylenediamine as diamine (b) was dissolved in 19 g of N-methylpyrrolidone in advance by cooling to 0 ° C. was added to the three-necked flask, and the stirring was continued. ) In the organic solvent solution (1-2), dicarboxylic acid halide and diamine were dissolved at the same time, but no precipitates or the like were observed even in this combination.
While stirring this organic solvent solution (1-2) up to 30 ° C. at a heating rate of 2 ° C./min, stirring (preliminary reaction) was performed for 1 hour at a rotational speed of 150 rpm while maintaining this temperature state. However, no precipitate that was seen as a synthetic reaction product was generated.
Next, an organic-inorganic composite was obtained by performing the same synthesis operation, washing treatment, and drying treatment using the same aqueous solution (2-2) as in Example 1.

(Example 3)
(Synthesis method of polyamide / zirconium oxide composite)
Obtained by adding 9.189 g of a zirconium carbonate carbonate aqueous solution “Zirmel 1000” manufactured by Nippon Light Metal Co., Ltd. as a metal compound (c-1) to 30 g of ion-exchanged water as an aqueous solution (2-3) and stirring at room temperature for 10 minutes. An organic-inorganic composite was obtained by performing the same synthetic operation, washing treatment and drying treatment as in Example 1 except that a colorless and transparent aqueous solution was used.

Example 4
(Synthesis method of polyamide / silica composite)
A colorless and transparent aqueous solution obtained by adding 9.737 g of water glass (sodium silicate) No. 3 as alkali silicate (c-2) to 30 g of ion-exchanged water as an aqueous solution (2-4) and stirring for 10 minutes at room temperature is used. An organic-inorganic composite was obtained by performing the same synthetic operation, washing treatment, and drying treatment as in Example 1 except that.

(Example 5)
(Synthesis method of polyamide / tin oxide composite)
Add 3.450 g of sodium stannate trihydrate (Na ₂ SnO ₃ .3H ₂ O) as a metal compound (c-1) to 40 g of ion-exchanged water as an aqueous solution (2-5) and stir at room temperature for 10 minutes. An organic-inorganic composite was obtained by performing the same synthetic operation, washing treatment and drying treatment as in Example 1 except that the colorless and transparent aqueous solution obtained was used.

(Example 6)
(Synthesis method of polyurea / aluminum oxide)
Using 19 g of toluene as an organic solvent, 1.435 g of triphosgene as a phosgene compound as a monomer (a) in this organic solvent was placed in a 50 cm ³ three-necked flask and stirred while cooling to 15 ° C. using cooling water in a nitrogen stream. Dissolved. Next, an organic solvent in which 3.104 g of 4,4-diaminodiphenylmethane was dissolved in toluene was cooled to 15 ° C. and then added to a three-necked flask, and stirring was continued to obtain an organic solvent solution (1-6). In the organic solvent solution (1-6), the phosgene compound and the diamine were simultaneously dissolved, but no generation of precipitates was observed. Next, the organic solvent solution (1-6) was heated to 55 ° C. at a heating rate of 2 ° C./min while stirring and stirred for 1 hour at a rotational speed of 150 rpm while maintaining this temperature state (preliminary reaction). However, no precipitate that was seen as a synthetic reaction product was generated. Next, using the same aqueous solution (2-6) as in Example 1, the same synthesis operation, washing treatment, and drying treatment were performed to obtain an organic-inorganic composite.

(Example 7)
(Synthesis of polyurethane / silica composite)
18 g of acetone was used as an organic solvent, and 4.943 g of 2,2-bis (4-chloroformoxylphenyl) propane, which is a chloroformate compound as a monomer (a), was added to this organic solvent in a 50 cm ³ three-necked flask. After stirring and dissolving at room temperature under an air stream, the outer periphery of the flask was cooled to 15 ° C. with cooling water. Next, an organic solvent in which 1.514 g of paraphenylenediamine was dissolved in 18 g of acetone was cooled to 15 ° C., and then added to a three-necked flask, and stirring was continued to obtain an organic solvent solution (1-7). In the organic solvent solution (1-7), the chloroformate compound and the diamine were simultaneously dissolved, but no generation of precipitates or the like was observed. Next, this organic solvent solution (1-7) was heated to 45 ° C. at a rate of 2 ° C./min while stirring, and stirred for 1 hour at a rotational speed of 150 rpm while maintaining this temperature state (preliminary reaction). However, no precipitate that was seen as a synthetic reaction product was generated. Next, 5.138 g of water glass No. 1 as sodium silicate (c-2) was added to 30 g of ion-exchanged water and stirred at room temperature for 10 minutes to obtain a uniform aqueous solution (2-7). While stirring the organic solvent solution (1-1) in the three-necked flask at 150 rpm using a stirring blade, the aqueous solution (2-7) was added dropwise over 10 seconds. As the aqueous solution (2-7) was added dropwise, the precipitate gradually precipitated. When the dropping of the aqueous solution was completed, the stirring rotation speed was increased to 200 rp, and stirring was continued for 30 minutes in this state to obtain a slurry containing a light yellow powdery composite. Then, the organic inorganic composite was obtained by performing the washing | cleaning process and drying process similar to Example 1. FIG.

Examples 8 to 9 show a method for producing an organic-inorganic composite containing two inorganic components.
(Example 8)
(Synthesis Method of Polyamide / Aluminum Oxide / Zinc Hydroxide Composite: Supporting Inorganic Second Component in Example 1)
An organic solvent solution (1-8) cooled at 0 ° C. having the same composition as that used in Example 1 was prepared. The monomer was prepolymerized in the organic solvent solution (1-8) by heating at the same rate of temperature increase as in Example 1 and stirring at 30 ° C. for 1 hour. Next, 2.504 g of powdered sodium aluminate P-100 manufactured by Asada Chemical Industry Co., Ltd. as a metal compound (c-1) was added to 35 g of ion-exchanged water, and the mixture was stirred at room temperature for 10 minutes. Into this aqueous solution, 0.126 g of zinc hydroxide as a metal compound (c-3) was added and stirred at room temperature for 20 minutes to obtain a uniform transparent aqueous solution (2-8). An organic-inorganic composite slurry was obtained by the same synthetic operation as in Example 1 except that these were used. In this example, the filtrate generated when the obtained composite slurry was filtered off was collected and dried with hot air at 150 ° C. for 5 hours, and the remaining powder was subjected to fluorescent X-ray measurement described later. Other than this, the organic-inorganic composite was obtained by performing the washing | cleaning process and the drying process similar to Example 1. FIG.

Example 9
(Synthesis Method of Polyamide / Silica / Tungsten Oxide Composite: Supporting Inorganic Second Component in Example 4)
After preparing an organic solvent solution (1-9) cooled at 0 ° C. having the same composition as that used in Example 1, prepolymerization by heating similar to Example 1 was performed. Next, 9.737 g of water glass (sodium silicate) No. 3 as alkali silicate (c-9) was added to 30 g of ion-exchanged water, and the colorless and transparent aqueous solution obtained by stirring for 10 minutes at room temperature was heated to 60 ° C. Then, 0.126 g of tungsten oxide was added as a metal compound (c-3) and stirred at room temperature for 20 minutes to obtain a uniform transparent aqueous solution. This was cooled to 0 degreeC and it was set as the aqueous solution (2-9). An organic-inorganic composite was obtained by performing the same synthetic operation, filtrate recovery, washing treatment, and drying treatment as in Example 9 except that these were used.

(Comparative Example 1: Preparation of organic-inorganic composite by melt-kneading method, equivalent to comparison of Example 2)
Totally aromatic polyamide powder and aluminum oxide (alumina) fine particles by a melt kneading method under the following conditions using a lab plast mill C type, KF-15 mixer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), which is a resin melt kneading apparatus. And a kneading test. This comparative example has a composition corresponding to the comparative test of Example 2.
Mixing specimen: 8.0 g of Kevlar (aromatic polyamide) resin powder, nano-alumina fine particles (CAI) while rotating the kneading blade at a mixer rotation speed of 10 rpm in a kneading chamber heated to a heating temperature of 350 ° C. (maximum temperature at which the mixer can be used) Chemical blend, average particle size 31nm) 2.0g was dry blended and introduced, but because Kevlar's melting point is 500 ° C or higher, much higher than the heating temperature, the resin does not melt and the melt kneading operation itself is impossible. there were. In addition, since the thermal decomposition point of Kevlar is lower than the melting point of 450 ° C., it is impossible to produce an organic-inorganic composite having the present polymer component by melt kneading operation even if there is an apparatus capable of kneading at a higher temperature. It was concluded.

(Reference Example 1: Experiment corresponding to Example 1)
(Synthesis method of polyamide / aluminum oxide composite without preheating polymerization)
An organic solvent solution (1-S1) cooled at 0 ° C., which is an organic solvent solution having the same composition as in Example 1, was obtained, and 0.1 g of the liquid was sampled immediately, and the molecular weight distribution was determined by the method described later (Measurement 1). It used for the measurement. Next, an aqueous solution (2-S1) in which an aqueous solution having the same composition as that of Example 1 prepared in advance was cooled to 0 ° C., and these raw material solutions were used. The organic-inorganic composite was obtained by performing a drying process. In the organic solvent solution (1-S1), as a result of molecular weight distribution measurement, a material having a molecular weight of 300 or more was not detected, and it was found that the oligomerization reaction did not proceed.

(Reference Example 2: Experiment corresponding to Example 2)
(Synthesis method of polyamide / aluminum oxide composite without preheating polymerization)
After obtaining an organic solvent solution (1-S2) cooled at 0 ° C. having the same composition as in Example 2, the heating treatment was not performed as in Reference Example 1. Next, a synthetic operation similar to that in Example 1 was performed except that an aqueous solution (2-S2) prepared in advance and then cooled to 0 ° C. was used, and that these raw material solutions were used. The organic-inorganic composite was obtained by performing washing treatment and drying treatment.

(Reference Example 3: Experiment corresponding to Example 3)
(Synthesis of polyamide / zirconium oxide composite without preheating polymerization)
An organic solvent solution (1-S3) cooled at 0 ° C. having the same composition as in Example 3 was obtained. Using this and an aqueous solution (2-S3) prepared in advance and cooled to 0 ° C. after obtaining an aqueous solution having the same composition as in Example 3, the same synthesis operation, washing treatment, and drying treatment as in Example 1 are performed. Thus, an organic-inorganic composite was obtained.

(Reference Example 4: Experiment corresponding to Example 4)
(Synthesis method of polyamide / silica composite without preheating polymerization)
An organic solvent solution (1-S4) cooled to 0 ° C. having the same composition as in Example 4 was obtained. Using this and an aqueous solution (2-S4) prepared in advance and cooled to 0 ° C. after obtaining an aqueous solution having the same composition as in Example 4, the same synthesis operation, washing treatment and drying treatment as in Example 1 are performed. Thus, an organic-inorganic composite was obtained.

(Example 5: Experiment corresponding to Example 5)
(Synthesis method of polyamide / tin oxide composite without preheating polymerization)
An organic solvent solution (1-S5) cooled at 0 ° C. having the same composition as in Example 5 was obtained. Using this and an aqueous solution (2-S5) prepared in advance and cooled to 0 ° C. after obtaining an aqueous solution having the same composition as in Example 5, the same synthesis operation, washing treatment, and drying treatment as in Example 1 are performed. Thus, an organic-inorganic composite was obtained.

(Reference Example 6: Experiment corresponding to Example 6)
(Synthesis of polyurea / aluminum oxide without preheating polymerization)
An organic solvent solution (1-S6) cooled to 0 ° C. having the same composition as in Example 6 was obtained. Using this and an aqueous solution (2-S6) prepared in advance and cooled to 0 ° C. after obtaining an aqueous solution having the same composition as in Example 6, the same synthesis operation, washing treatment and drying treatment as in Example 1 are performed. Thus, an organic-inorganic composite was obtained.

(Reference Example 7: Experiment corresponding to Example 7)
(Synthesis method of polyurethane / silica composite without preheating polymerization)
An organic solvent solution (1-S7) cooled to 0 ° C. having the same composition as in Example 7 was obtained. Using this and an aqueous solution (2-S7) prepared in advance and cooled to 0 ° C. after obtaining an aqueous solution having the same composition as in Example 7, the same synthesis operation, washing treatment and drying treatment as in Example 1 are performed. Thus, an organic-inorganic composite was obtained.

(Measurement 1) Measurement of molecular weight of material in organic solvent solution (1) 0.1 g of organic solvent solution (1) collected immediately before mixing aqueous solution (2) in Example 1 and Comparative Example 1 was added to NN-dimethyl. Diluted with 30 g of acetamide. The molecular weight distribution of polystyrene was measured by introducing NN-dimethylacetamide as a solvent into Nippon Waters TYPE 2487 and 2414 detectors, which are molecular weight distribution measuring devices (GPC).

  Next, the following items were measured and tested for the organic-inorganic composites obtained in the above Examples and Reference Examples. In addition, about each comparative example, the sample which can be used for evaluation was not obtained.

(Measurement 2) Method for Measuring Content of Inorganic Compound The organic-inorganic composite was completely dried and then precisely weighed (composite mass), and this was baked in air at 600 ° C. for 2 hours to completely burn out the polymer component, and then baked The latter mass was measured and used as the ash mass. The ash content was calculated from the following formula.

At this time, the amount of the metal compound (c-3) present in the complex is about 100% from the analysis of the metal compound derived from the metal compound (c-3) in the filtrate described later. It is known from the amount of c-3). Therefore,

が成り立つ。

Holds.

(Measurement 3) Verification of inorganic components (measurement with fluorescent X-rays)
About 1 g of the organic-inorganic composite powder was set in a measurement holder having an opening of 10 mm in diameter, and used as a measurement sample. The sample was subjected to total elemental analysis using a fluorescent X-ray analyzer “ZSX100e” manufactured by RIKEN ELECTRIC CO., LTD. Using the results of the total elemental analysis obtained, the sample data of the sample for measurement (the data given is sample shape; film, correction component; cellulose, mass value per area of the measured sample) is given to the apparatus, The element presence ratio in the complex was calculated by the FP method (Fundamental Parameter method; a method in which the uniformity of the sample and surface smoothness are assumed, and correction is performed using constants in the apparatus to quantify the components).

The organic-inorganic composite obtained in any of the examples is also composed of a metal compound (c-1), an inorganic element derived from alkali silicate (c-2) (aluminum in the case of sodium aluminate, zirconium in the case of potassium zirconium carbonate). In the case of sodium stannate, tin was detected, and in the case of sodium silicate (water glass), silicon) was detected, indicating that the target inorganic compound was complexed. In Examples 8 and 9, metal (Zn, W) derived from the metal compound (c-3) was also detected. In the samples obtained in any of the examples, the amount of the metal compound (c-3) obtained by this method was within the error range of 0.1% by mass to the aqueous solution (2) (c-3). ) And the predicted value calculated from the charged amount.
On the other hand, metal compound (c-1) which is an inorganic raw material, alkali metal element derived from alkali silicate (c-2) (sodium in the case of sodium silicate, sodium aluminate and sodium stannate, potassium in the case of potassium zirconium carbonate) ) Was detected only to the extent of traces. Therefore, the ash (that is, the inorganic substance) obtained by the measurement method of the inorganic compound fine particles of (Measurement 2) does not substantially contain an alkali metal. In the present invention, the metal compound (c-1), the alkali silicate ( It was revealed that the alkali metal removal and solidification reaction from c-2) was performed according to the predicted reaction mechanism.
In addition, from the dried products of the filtrates of Examples 8 and 9, only impurity elements such as Fe were detected in addition to NaCl as a reaction by-product, and the metal elements corresponding to the metal compound (c-3) were Not detected. From this, it became clear that the metal compound (c-3) was supported on the composite by the synthesis operation of the composite.

(Measurement 4) Verification of polymer components (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 any of the examples, an absorption peak corresponding to the target polymer (for example, a peak corresponding to C═O stretching vibration near 1800 cm ⁻¹ and N—H stretching near 1540 cm ^{−1 in} polyamide) appears clearly. It was confirmed that the components were well synthesized.

(Transmission electron microscope (TEM) observation and element mapping)
The organic-inorganic composite was hot-pressed for 2 hours under the conditions of 170 ° C. and 20 MPa / cm ² to obtain a flake made of an organic-inorganic composite having a thickness of about 1 mm. This was made into an ultrathin slice having a thickness of 75 nm using a focused ion beam apparatus. Based on TEM photographs of 500,000 times each, using “JEM-2010EFE” (manufactured by JEOL Ltd.), which is an energy filter TEM capable of elemental mapping by EDS elemental analysis simultaneously with TEM observation of the obtained sections. Elemental mapping was performed. The inorganic main component was confirmed about Examples 1-8 from the element kind shown by mapping. In Examples 9 and 10, the inorganic main component and the metal compound (c-3) were distinguished. By this element mapping, the measurement of the inorganic main component described later (Measurement 4), the particle size measurement of the metal compound (c-3), and the supported state of the metal compound (c-3) described later (Measurement 5) on the inorganic main component Was observed.

(Measurement 5) Measurement of particle size of inorganic main component The particle size of the inorganic main component or metal compound (c-3) was determined by measuring 100 particle sizes from a TEM photograph, and taking the average value as the average particle size. In addition, the measuring method of the particle size was performed as follows according to the particle shape.
When the particles are substantially spherical: The length of an arbitrary side is defined as the particle size of the particles. When the inorganic main component was zirconium oxide, tin oxide or silica, and the metal compounds (c-3) of Examples 8 and 9 were measured by this method.
When the particles have an aspect ratio of 2 or more: The lengths of the major axis and minor axis of the particle were measured, and the value of (major axis + minor axis) / 2 was defined as the particle diameter of the particle. When the inorganic main component was aluminum oxide, it was measured by this method.

(Measurement 6) Confirmation of presence or absence of aggregates on the surface of the metal compound (c-3) Samples obtained by vapor-depositing carbon with a thickness of 10 nm on the organic-inorganic composite particles in each Example and Comparative Example Then, elemental mapping for the metal compound (c-3) was performed using an electrolytic emission scanning electron microscope “SEM-EDX” manufactured by Hitachi, and the dispersion state of the supported metal was measured. The resolution of the metal size in this measurement method is 1 μm. When coarse particles of 1 μm or more were produced, there was an agglomerate, and there was no agglomerate if there was.

  Table 1 summarizes the results of Examples 1 to 7, Table 2 summarizes the results of Examples 8 to 9, and Table 3 summarizes the above measurement results of Reference Examples 1 to 7.

  In the present invention, after allowing the diamine and the monomer (a) to coexist in the organic solvent at a temperature of 25 ° C. or less, the polymerization reaction is held so that only a certain amount proceeds, and oligomerized, By promoting these polymerization reactions by adding an inorganic raw material containing an alkali metal dissolved in water, a bottom-up organic-inorganic composite could be synthesized. Moreover, the obtained organic-inorganic composite was as shown in Table 1 (that is, the organic-inorganic composite obtained in Examples 1 to 8) polyamide, polyurea, polyurethane with an inorganic compound having a size of 80 nm or less, and 20 In addition to being dispersed at a high content of at least mass%, almost no alkali metal derived from inorganic component raw materials was detected.

The effect of the prepolymerization by heating the organic solvent solution (1) can be clarified by comparison with the particle size in each reference example shown in Table 3. In any of the examples, the inorganic particle size could be reduced as compared with the reference example. In particular, the effect of this prepolymerization was high in the case of inorganic components (ZrO ₂ , SnO ₂ ) whose particle diameter exceeded 100 nm in the reference example. Both ZrO ₂ and SnO ₂ are known to have a faster inorganic precipitation reaction than SiO ₂ , and it is considered that atomization could be achieved in the present invention because these unilateral aggregations could be prevented. Moreover, the difference of the inorganic content rate by the presence or absence of prepolymerization was hardly seen.

  The organic-inorganic composite obtained in the present invention can be processed by a process such as press molding, and can be used as various structural materials. In addition, the obtained organic-inorganic composite is melt-kneaded and added to another resin, so that the strength, elastic modulus, impact resistance, electron conductivity, charging due to the inorganic main components in the composite are added to the resin. Properties such as prevention properties can be imparted. At this time, since the inorganic particle diameter is extremely small, a high addition effect can be expected. In addition, it is possible to simultaneously impart a function that can act effectively even in a small amount such as catalytic properties and antibacterial / antifungal properties due to the metal compound (c-3) as the inorganic second component.

Claims (4)

An organic solvent solution (1) containing at least one monomer (a) selected from the group consisting of a dicarboxylic acid halide, a dichloroformate compound, and a phosgene compound, and a diamine (b);
Contains a metal compound (c-1) having two or more metal elements including at least one alkali metal selected from the group consisting of metal oxides, metal hydroxides and metal carbonates, and alkali silicate (c-2) An aqueous solution (2)
The monomer (a) and the diamine (b) are partially reacted by heating the organic solvent solution (1) and then mixed, and the organic solvent solution (1) and the aqueous solution (2) are combined. An organic-inorganic composite characterized in that at least a part thereof is kept in a compatible state or coexisted in a separated state, and the reaction between the monomer (a) and the diamine (b) is further advanced and at the same time, the inorganic component is precipitated. Body manufacturing method. The organic inorganic solution according to claim 1, wherein the temperature before heating of the organic solvent solution (1) is in the range of -30 ° C to 15 ° C, and the temperature after heating is in the range of 25 ° C to 60 ° C. A method for producing a composite. The method for producing an organic-inorganic composite according to claim 1 or 2, wherein the diamine (b) is an aromatic diamine. The method for producing an organic-inorganic composite according to any one of claims 1 to 3, wherein the aqueous solution (2) contains a metal compound (c-3) dissolved in a basic aqueous solution and precipitated in a neutral solution. .