JP2012149207A - Method for producing organic-inorganic composite, and organic-inorganic composite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing conveniently obtaining an organic-inorganic composite including a semi-aromatic polyester as an organic ingredient.SOLUTION: In the method for producing an organic-inorganic composite, an organic solvent solution (1) containing an aromatic dicarboxylic acid halide (a), and an aqueous solution (2) containing at least one inorganic compound (B) selected from a group composed of a metal compound (b-1) having two or more metal elements including at least one alkali metal and selected from a group composed of a metal oxide, a metal hydroxide, and a metal carbonate, an alkali silicate (b-2), and a clay mineral (b-3), are made to coexist with each other in a state in which a diol (c) is contained in either one or both of the organic solvent solution (1) and the aqueous solution (2), while the organic solvent solution (1) and the aqueous solution (2) being kept in such a way that they are at least partly dissolved in each other, or being separated from each other, and the aromatic dicarboxylic acid halide (a) and the diol (c) are made to react with each other, and simultaneously the inorganic ingredient is deposited.

Description

  The present invention relates to a method for producing an organic-inorganic composite using a semi-aromatic polyester 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.

  The inventors have previously invented and disclosed a method for synthesizing an organic-inorganic composite containing a polymer such as polyamide, polyurea or polyurethane as a matrix polymer and containing nano-sized inorganic fine particles at a high filling rate. For example, Patent Document 1 describes a method for producing an organic-inorganic composite of clay and polyamide, in which diamine is dissolved in water in which clay having an alkali metal component is dispersed, and a dicarboxylic acid halide dissolved in an organic solvent is reacted. Has been. Patent Document 2 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 3 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 of an oxide and polyamide, polyurea, polyurethane or the like is described.

  In the above method, diamine and a monomer such as dicarboxylic acid halide that reacts with diamine are reacted to synthesize an organic polymer, while an inorganic component is precipitated or synthesized from a dissolved state, and the organic polymer and the inorganic material are complementarily precipitated. By doing so, an inorganic component having a nano particle diameter can be precipitated.

  However, in the above method, since the raw material monomer to be dissolved in water is only diamine, the obtained matrix polymer is limited to polyamide, polyurea and polyurethane. If the variation of the polymer component of the organic-inorganic composite can be expanded, the application of the composite material can be further expanded. In particular, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN) are widely used as general-purpose polymers and relatively inexpensive engineering plastics, so these semi-aromatic polyesters are used as polymer components. If there is an organic-inorganic composite, it can be expected to improve various functions by mixing it with semi-aromatic polyesters and combining the inorganic components.

  An organic-inorganic composite formed by blending a semi-aromatic polyester with a layered structure composed of at least one metal compound selected from alkoxysilanes and metal halides, organometallic compounds and metal alkoxysides is described in Patent Document 4. ing. However, the organic-inorganic composite includes a method of polymerizing the semi-aromatic polyester raw material or semi-aromatic polyester precursor by adding the layered structure, a method of melt-kneading the semi-aromatic polyester and the layered structure, Alternatively, the layered structure and the semi-aromatic polyester are blended by a method of mixing in a solvent or the like (see paragraph 0074), and there is a limit to the uniformity of the obtained organic-inorganic composite.

JP-A-9-208291 JP-A-10-176106 JP 2005-036211 A Japanese Patent Laid-Open No. 2004-307708

  The problem to be solved by the present invention is to provide a production method for easily obtaining an organic-inorganic composite having a semi-aromatic polyester as an organic component.

  The inventor has an organic solvent solution (1) containing an aromatic dicarboxylic acid halide (a), an aqueous solution (2) containing an alkali metal, an alkali silicate or a clay mineral, the organic solvent solution (1) and The aromatic dicarboxylic acid halide (a) is prepared by allowing the organic solvent solution (1) and the aqueous solution (2) to coexist in a state where the diol (c) is contained in one or both of the aqueous solutions (2). And the diol (c) were reacted to synthesize a semi-aromatic polyester, and at the same time, an organic-inorganic composite in which an inorganic component was deposited was found to be obtained.

  That is, the present invention includes an organic solvent solution (1) containing an aromatic dicarboxylic acid halide (a) and at least one alkali metal selected from the group consisting of metal oxides, metal hydroxides and metal carbonates. An aqueous solution containing at least one inorganic compound (B) selected from the group consisting of a metal compound (b-1) having one or more metal elements, an alkali silicate (b-2), and a clay mineral (b-3) ( 2) and the organic solvent solution (1) and the aqueous solution (2) in a state where the diol (c) is contained in one or both of the organic solvent solution (1) and the aqueous solution (2). An organic-inorganic composite in which at least a part of the aromatic dicarboxylic acid halide (a) reacts with the diol (c) and at the same time precipitates an inorganic component while keeping at least partially compatible or separated. To provide a production method.

  Moreover, this invention provides the organic inorganic composite with which the content rate of the inorganic component in 100 mass% obtained by the manufacturing method of the said organic inorganic composite is 10-60 mass%.

  According to the present invention, an organic-inorganic composite having a semi-aromatic polyester as a matrix polymer can be easily obtained.

  Further, the present invention can use raw materials such as alkali aluminate, alkali silicate, and alkali-containing metal clay as raw materials for inorganic compounds to be combined, and inexpensive diols such as ethylene glycol as raw materials for organic components. It's cheap. In addition, the production can be performed in one step in a short time using a general-purpose stirring device.

(Organic solvent solution (1))
The organic solvent solution (1) used in the present invention contains at least an aromatic dicarboxylic acid halide (a) and an organic solvent.

(Aromatic dicarboxylic acid halide (a))
The dicarboxylic acid halide used in the present invention essentially comprises an aromatic dicarboxylic acid halide (a). Examples of aromatic dicarboxylic acid halides (a) include aromatic halides of aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, or hydrogens of these aromatic rings substituted with halogen atoms, nitro groups, alkyl groups, etc. Examples thereof include acid halides of aromatic dicarboxylic acids and acid halides of dicarboxylic acids composed of a plurality of aromatic rings (for example, naphthalene, anthracene skeleton, etc.).
In addition to the aromatic dicarboxylic acid halide (a), an aliphatic dicarboxylic acid halide (for example, an acid halide of an aliphatic dicarboxylic acid such as malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, etc.) They can be mixed. However, since the aliphatic carboxylic acid halide has a significantly higher reactivity with water than the aromatic carboxylic acid halide (a), it undergoes a hydrolysis reaction with water present in a large excess in the aqueous solution (2) to be described later, resulting in a dicarboxylic acid. Side reactions that produce acid halides may occur very rapidly. Once dicarboxylic acid is formed, polyester cannot be obtained because reaction with diol does not occur near room temperature. Accordingly, the content of the aliphatic carboxylic acid halide is preferably 30 mol% or less, and most preferably 10 mol% or less, based on the total amount of the dicarboxylic acid halide used in the present invention.

(Organic solvent)
The organic solvent used in the present invention is not particularly limited as long as the aromatic dicarboxylic acid halide (a) can be dissolved in a necessary amount. Specific examples include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as n-hexane, ethers such as tetrahydrofuran, dimethyl ether, diethyl ether, dibutyl ether, and anisole. Tells, ketones such as acetone, 2-butanone, cyclohexanone, alkyl acetates such as ethyl acetate, propyl acetate, butyl acetate, halogenated hydrocarbons such as chloroform, methylene chloride, n-methylpyrrolidone, NN-dimethyl Examples thereof include nitrogen-containing organic solvents such as acetamide and dimethylformamide, propylene carbonate, dimethyl sulfoxide, and the like. These may be used in combination.

  The total monomer concentration of the dicarboxylic acid halide containing the aromatic dicarboxylic acid halide (a) in the organic solvent solution (1) is not particularly limited as long as the polymerization reaction proceeds sufficiently. Therefore, a concentration range of 0.01 to 3 mol / L, particularly 0.05 to 1 mol / L is preferable.

(Aqueous solution (2))
The aqueous solution (2) used in the present invention is a metal compound (b-) having two or more metal elements containing at least one alkali metal selected from the group consisting of at least a metal oxide, a metal hydroxide, and a metal carbonate. 1) Alkali silicate (b-2) or clay mineral (b-3) is contained. These are raw materials for inorganic components of the organic-inorganic composite in the present invention.

(Metal compound (b-1), alkali silicate (b-2) or clay mineral (b-3))
The raw material of the inorganic component of the organic-inorganic composite in the present invention is an inorganic compound containing an alkali metal. Specifically, a metal compound (b-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 ( abbreviated as b-1), alkali silicate (b-2) or clay mineral (b-3) is preferred because it is readily available and inexpensive. When the metal compound (b-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 (b-2) is used as a raw material, silica (silicon dioxide) is precipitated. In addition, when the clay mineral (b-3) is used as a raw material, a clay mineral having at least a portion of the layer cleaved is combined. (Hereinafter, "metal compound (b-1), alkali silicate (b-2) or clay mineral (b-3)" may be abbreviated as "inorganic compound (B)")

(Metal compound (b-1))
The metal compound (b-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 (such as Na1.6Al0.9O2.8 for example) in complex oxide-based inorganic materials, neither xyz nor integers or decimals can be defined. Point to.)
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 to precipitate is a compound which hardly or not dissolves in water and the organic solvent used in the organic solvent solution (1).

  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 (b-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, zirconium zirconium carbonate, cobalt potassium carbonate, and potassium tin carbonate. Is mentioned.
The metal compound (b-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 (b-1), alkali aluminate, alkali stannate, zinc zincate, and zirconium carbonate alkali are particularly preferably used. Since these metal compounds have high water solubility and strong basicity when dissolved, the reaction between the aromatic dicarboxylic acid halide (a) and the diol (c) is likely to proceed. Of these, alkali aluminates are most preferably used because they are particularly water-soluble and inexpensive.

  In addition, when there is no commercially available material for the metal compound (b-1), for example, a soluble metal compound is dissolved in a high concentration aqueous solution of sodium hydroxide or alkali metal hydroxide of potassium hydroxide. To obtain the metal compound (b-1). Thereby, the kind of inorganic material which can be combined can be expanded. Metal compounds that can be used here include zinc hydroxide, aluminum hydroxide, antimony (III) hydroxide, antimony (V), iridium hydroxide (III), iridium hydroxide (IV), gold hydroxide (III), chromium hydroxide (III), cobalt hydroxide (II), tin hydroxide (II), nickel hydroxide (II), tantalum hydroxide (V), niobium hydroxide (V), nickel hydroxide (II), palladium hydroxide (II), metal hydroxides such as beryllium hydroxide, zinc oxide (II), antimony (III) oxide, antimony oxide (V), gallium oxide (I), gold (III) oxide , Gold oxide hydroxide (III), lead oxide hydroxide (II), tin oxide (II), tin oxide (IV), tungsten oxide (VI), titanium oxide (IV), lead oxide (II), lead oxide ( IV), niobium oxide (V), vanadium oxide (III)), vanadium oxide (IV) Vanadium oxide (V), bismuth oxide (V), molybdenum oxide (VI), ruthenium oxide (VIII), rhenium oxide (VI) and other oxides, zinc carbonate, lead carbonate (II), basic copper carbonate (II) And the like.

(Alkali silicate (b-2))
The alkali silicate (b-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, where 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.

(Clay mineral)
Since the clay mineral (b-3) used in the present invention is dissolved in the aqueous solution (2) and used, it must be soluble in water, swellable, and dispersible. In particular, a clay mineral having an alkali metal ion layer is preferable. Among them, a clay mineral in which the alkali metal is sodium is most preferably used because it is highly soluble in water and swellable and inexpensive. These clay minerals swell or finely disperse in water and show alkalinity. The alkali metal between the clay layers also promotes the reaction between the aromatic dicarboxylic acid halide (a) and the diol (c). As the alkali metal between the clay layers, clay mineral (Na-type clay mineral) which is Na is preferable because it has the highest swelling property with respect to water.

  Particularly preferred as the clay structure is a smectite group. Among them, montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, stevensite, etc. can be exemplified more specifically. In addition to these, vermiculite or the like may be used.

(Solvent of aqueous solution (2))
The compound (B) is dissolved in water and used as an aqueous solution (2). When the reaction with the organic solvent solution is performed in a compatible state, a polar organic solvent such as acetone, tetrahydrofuran or acetonitrile is mixed up to about 30% by mass of the aqueous solution (2) to adjust the solubility. May be. Moreover, in order to accelerate | stimulate reaction in aqueous solution (2), you may dissolve basic substances, such as an alkali hydroxide and an alkali carbonate. Moreover, in order to improve mixing property with the organic solvent solution (1), additives such as a surfactant may be contained.

  Plural inorganic components (In the present invention, “inorganic component” refers to an inorganic compound that does not contain an alkali metal deposited by the method for producing an organic-inorganic composite of the present invention. In addition, the inorganic compound (B) is used as a raw material. The obtained inorganic component is referred to as “inorganic component (B)”) in the case where the organic-inorganic composite is desired to contain the metal compound (b-1), the alkali silicate (b-2), or the clay. Mineral (b-3) may be used in combination. However, depending on the combination, the inorganic compound (B) may gel or precipitate in the aqueous solution (2) and the inorganic component (B) may not be able to be combined in a fine particle state. Need attention.

  Further, by adding the metal compound (b-4) that dissolves in the basic aqueous solution and precipitates in the neutral solution to the aqueous solution (2), the inorganic component of the organic-inorganic composite is diversified to further function. There are methods that can be granted. In this method, any one of the compounds (b-1), (b-2) and (b-3) is consumed with the reaction of the diol (c) and the aromatic dicarboxylic acid halide (a). This utilizes the fact that the pH of the aqueous solution changes from basic to neutral. That is, since the aqueous solution is basic at the initial stage of the complex synthesis reaction, the metal compound (b-4) remains in a dissolved state, but when the organic-inorganic complexing reaction proceeds and the aqueous solution approaches neutrality, the metal compound (B-4) precipitates. Thus, unlike the inorganic component (B), the metal compound (b-4) is compounded with substantially the same composition as the raw material. Therefore, the obtained organic-inorganic composite has a structure in which the inorganic component (B) is uniformly dispersed in the polymer matrix and the metal compound (b-4) is supported on the inorganic main component on the outermost surface. .

  Examples of metal compounds that can be suitably used as such a metal compound (b-4) include alkali metals and alkaline earth metal compounds such as lithium phosphate and magnesium hydroxide, tungsten (VI) oxide, vanadium oxide (V ), Cobalt oxide (II), cobalt hydroxide (II), cobalt oxalate (II), niobium oxide (II), iron hydroxide (II), niobium oxide (V), molybdenum oxide (VI), manganese hydroxide (II), gold oxide (III), gold hydroxide (III), silver iodate (I), silver carbonate (I), silver oxide (I), silver sulfide (I), copper oxide (I), hydroxylated Copper (II), basic copper carbonate (II), copper oxide (II), copper phosphate (II), copper oxalate (II), rhenium oxide (VI), palladium hydroxide (II), ruthenium hydroxide ( IV) transition metal compounds, tin oxide (II), tin hydroxide (II), aluminum hydroxide, aluminum phosphate Minium, indium (III) hydroxide, nickel (II) oxalate, zinc (II) oxide, zinc (II) hydroxide, zinc (II) oxalate, antimony (III) oxide, gallium (III) oxide, lead oxide Typical metal compounds such as (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.

(Temperature of aqueous solution)
The temperature of the aqueous solution (2) is not particularly limited as long as the various materials can be dissolved without any problem. Most preferably, it is near room temperature where it can be used easily.

(Diol (c))
Examples of the diol (c) used in the present invention include 1,2-ethanediol (ethylene glycol), 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,8-octanediol. In addition to glycols having a divalent hydroxyl group of aliphatic diols such as methylpentanediol and dimethylbutanediol, and cycloaliphatic aliphatic diols such as cyclohexanedimethanol, 1,3-benzenedimethanol and 1,4-benzene In addition to dimethanol, examples include hydroquinone, resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, bisphenol F, and aromatic diols of ethylene oxide extensions of aromatic polyphenols such as tetramethylbiphenol.

(Diol (c) solution)
The diol (c) may be dissolved in the organic solvent solution (1) or in the aqueous solution (2). It may be dissolved in both. In the present invention, it is preferable to add the inorganic compound (B), which is a raw material of the inorganic component, to the reaction field in a completely dissolved state or a completely swollen state in order to make the inorganic component as complex as possible. When the diol (c) is dissolved in the aqueous solution (2), short-chain glycols such as ethylene glycol have high water solubility, and unlike the phenol component, they do not dissociate protons, so inorganic compounds such as alkali silicates and alkali aluminates ( The inorganic precipitation reaction in B) does not proceed. Further, even when dissolved in the organic solvent solution (1), the alcohol and the acid halide do not proceed under a condition where there is no alkali component near room temperature, so that the dissolved state can be maintained.

  Whether the diol (c) is dissolved in an organic solvent solution or an aqueous solution is appropriately selected from the viewpoint of the solubility of the diol (c) to be used in water and the organic solvent and the alkali strength of the inorganic raw material to be used. In general, from the viewpoint of contact between the reactive monomers, both the aromatic dicarboxylic acid halide (a) and the diol (c) tend to react more easily when dissolved in the organic solvent solution (1). A trifunctional polyol may coexist with the diol (c). Examples of polyols include 1,3,5-tris (2-hydroxyethyl) isocyanuric acid, 1,3,5-tris (2-hydroxypropyl) isocyanuric acid, glycerin, erythritol, pentaerythritol, dipentaerythritol, diethylene glycol, triethylene glycol, Aliphatic polyhydric alcohols such as ethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, tripropylene glycol, and triethanolamine may be used.

(Production method)
The method for producing an organic-inorganic composite of the present invention is at least selected from the group consisting of an organic solvent solution (1) containing an aromatic dicarboxylic acid halide (a), a metal oxide, a metal hydroxide, and a metal carbonate. At least one inorganic compound selected from the group consisting of a metal compound (b-1) having two or more metal elements including one alkali metal, an alkali silicate (b-2), and a clay mineral (b-3) ( B), the organic solvent solution (1) and the organic solvent solution (1) in a state where the diol (c) is contained in one or both of the organic solvent solution (1) and the aqueous solution (2). The aqueous solution (2) is kept at least partially compatible or coexisted in a separated state, and the aromatic dicarboxylic acid halide (a) and the diol (c) are reacted, and at the same time, an inorganic component is precipitated. And characterized in that.

  The reaction mechanism in the present invention is presumed as follows. In the diol (c), the proton in the hydroxyl group is partially ion-exchanged with the alkali metal ion generated when the inorganic compound (B) is dissolved in water to increase the reactivity. By contacting the aromatic dicarboxylic acid halide (a) in this state, the alkoxide derived from the diol (c) reacts with the aromatic acid halide (a) even at room temperature to produce a semi-aromatic polyester.

  At this time, as the inorganic compound (B), when a metal compound or alkali silicate is used, the alkali metal in the inorganic raw material is removed and at the same time, an inorganic polymerizing reaction, for example, silanol is used when alkali silicate is used. As the polycondensation reaction proceeds, an inorganic component is precipitated and an organic-inorganic composite is produced. On the other hand, when a clay mineral containing an alkali metal between layers is used as the inorganic compound (B), a part of the alkali metal ion that functions as a bonding material between layers is removed as an alkoxide when it is water-soluble or swollen with water. Therefore, the layers are separated from each other. If the semi-aromatic polyester is synthesized around this layer, the inorganic layer cannot be re-agglomerated, so it is estimated that the inorganic component is well dispersed. In addition, with the above reaction, alkali halides are generated as by-products, and these are discharged out of the synthesis system by dissolving in water in the synthesis system or water in the washing step.

(Method for coexistence of organic solvent solution (1) and aqueous solution (2))
In order for the organic solvent solution (1) and the aqueous solution (2) to coexist in a state where at least a part thereof is compatible or separated, the organic solvent solution (1) and the aqueous solution (2) are in contact with each other. The organic solvent solution (1) and the aqueous solution (2) are usually charged into one reaction kettle having a stirring blade. The reaction temperature is preferably near room temperature, and specifically in the range of 0 ° C to 50 ° C. Further, pressurization and decompression are not particularly required. The synthesis reaction of the organic-inorganic composite is usually completed in a short time of 30 minutes or less, although it depends on the monomer species, reaction apparatus, and scale used.

(Manufacturing equipment)
The production apparatus used in the present invention is not particularly limited as long as the production apparatus can satisfactorily contact and react the organic solvent solution (1) and the aqueous solution (2). Is possible. As a continuous type of specific device, “Fine Flow Mill FM-15” manufactured by Taihei Koki Co., Ltd., “Spiral Pin Mixer SPM-15” manufactured by the same company, or INDAG Machinenbaugmb Co., Ltd. "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 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 Faudler blade.

(Inorganic component of organic-inorganic composite)
The inorganic component of the organic-inorganic composite obtained by the production method of the present invention differs in shape and properties obtained from the metal compound (b-1), alkali silicate (b-2) or clay mineral (b-3) used. Therefore, what is necessary is just to select suitably according to the objective. For example, when the metal compound (b-1) is used, as the inorganic component, metal oxides such as aluminum oxide (alumina), tin oxide, zinc oxide, and zirconium oxide can be obtained. The raw materials for these metal oxides are alkali aluminate, alkali stannate, alkali zincate, and alkali zirconium carbonate. When alkali silicate (b-2) is used, silica is obtained as an inorganic component, and an organic-inorganic composite having a small inorganic particle size is obtained. Moreover, when a clay mineral (b-3) is used, the shape of an inorganic component has a high aspect ratio, and various functions can be imparted to the obtained organic-inorganic composite. The production method of the present invention is also characterized in that the particle size of the obtained inorganic component is small, and the organic-inorganic composite having an average particle size of 500 nm or less, more preferably 300 nm or less, and most preferably 5 nm to 100 nm. Can be obtained.

(Content ratio of inorganic component with respect to 100% by mass of organic-inorganic composite)
The inorganic component derived from the metal compound (b-1), the alkali silicate (b-2) or the clay mineral (b-3) of the organic-inorganic composite obtained in the present invention is the heat resistance and wear resistance of the inorganic material. And other properties such as surface hardness and heat dissipation properties.
Therefore, the content of the inorganic component with respect to the total amount of the organic-inorganic composite of 100% by mass is preferably a certain value, preferably 10-60% by mass, more preferably 15-60% by mass, and most preferably 30 to 60% by mass. If the content is too high, sheeting, processability to laminates, etc., or miscibility with other resins may be impaired.

Hereinafter, the present invention will be described with specific examples, but the present invention is not limited thereto. Unless otherwise indicated, “parts” and “%” are weight standards.
Examples 1 to 3 are examples in which the diol (c) is contained in the aqueous solution (2), and Examples 4 to 6 are examples in which the diol (c) is contained in the organic solvent solution (1).

Example 1
(Method for producing a reaction product of ethylene glycol / sodium aluminate / isophthalic acid chloride)
Acetone 52 g was used as an organic solvent, and 6.70 g of isophthalic acid chloride as an aromatic dicarboxylic acid halide (a) was stirred and dissolved in a 100 cm ³ beaker at room temperature with a stirrer to obtain an organic solvent solution (1-1). .
Next, in a 300 cm ³ three-necked flask, 2.05 g of ethylene glycol and 5.05 g of powdered sodium aluminate P-100 manufactured by Asada Chemical Industry Co., Ltd. as metal compound (b-1) are added to 66 g of ion-exchanged water. The mixture was stirred at 100 rpm with an anchor blade at room temperature for 10 minutes to obtain a transparent light yellow uniform aqueous solution (2-1). While stirring the aqueous solution at 150 rpm, the organic solvent solution (1-1) was added dropwise over 10 seconds. As the organic solvent solution was added dropwise, a white product quickly precipitated. When dropping of the organic solvent solution was completed, the stirring rotation speed was increased to 250 rpm, and stirring was continued at room temperature for 30 minutes to obtain a slurry containing a white powdery composite.

(Cleaning and drying of complex)
This slurry was placed on a 95 mmφ Nutsche filter paper with a mesh size of 4 μm and filtered under reduced pressure at 0.015 MPa to obtain a light yellow powdery liquid-containing organic-inorganic composite. This powder was dispersed in 200 g of ion-exchanged water, washed with water by stirring for 30 minutes at room temperature, and the dispersion was filtered by the same method as described above. Similar washing and filtration were repeated once more to obtain a water-containing organic-inorganic composite. This was dried with hot air at 150 ° C. for 5 hours to obtain white reactant-1.

(Example 2)
(Method for producing a reaction product of 1,4-butanediol / sodium aluminate / terephthalic acid chloride)
An organic solvent solution (1-2) was obtained in the same manner as in Example 1 except that 6.70 g of terephthalic acid chloride was used as the monomer (a). Next, a transparent and uniform aqueous solution (2-2) was obtained in the same manner as in Example 1 except that 2.98 g of 1,4-butanediol was used instead of ethylene glycol. This was stirred and mixed in the same manner as in Example 1 to obtain a slurry containing a white powdery composite. This was subjected to the same washing and drying treatment as in Example 1 to obtain white reactant-2.

(Example 3)
(Process for producing a reaction product of ethylene glycol / zinc oxide sodium hydroxide aqueous solution (sodium zincate aqueous solution) / isophthalic acid chloride)
As an aqueous solution of the metal compound (b-1), 4.0 g of zinc oxide was stirred in 20 g of an aqueous 38% by weight sodium hydroxide solution at room temperature for 60 minutes to completely dissolve the aqueous solution of sodium zincate. Next, the same organic solvent solution (1-3) as in Example 1 was prepared.
Next, a transparent and uniform aqueous solution (2-3) was obtained in the same manner as in Example 1 except that 2.09 g of the aqueous solution of sodium zincate was used instead of sodium aluminate. This was mixed in the same manner as in Example 1 to obtain a slurry containing a white powdery composite. This was subjected to the same washing and drying treatment as in Example 1 to obtain a white reactant-3.

Example 4
(Method for producing a reaction product of ethylene glycol / water glass No. 3 / isophthalic acid chloride)
Acetone 52 g was used as an organic solvent, 6.70 g of isophthalic acid chloride as aromatic dicarboxylic acid halide (a), and 2.05 g of ethylene glycol as diol (c) were placed in a 300 cm ³ three-necked flask, and 100 rpm by an anchor blade. Was stirred for 10 minutes to obtain a transparent and uniform organic solvent solution (1-4). Next, 66 g of water was put into a 200 cm ³ beaker, 22.6 g of water glass No. 3 was added, and the mixture was stirred with a stirrer for 10 minutes to obtain a uniform transparent aqueous solution (2-4). While stirring the organic solvent solution (1-4) at 150 rpm, the aqueous solution (2-4) was added dropwise over 10 seconds. As the aqueous solution was dropped, a white product was quickly deposited. When the dropping of the aqueous solvent solution was completed, the stirring rotational speed was increased to 250 rpm, and stirring was continued for 30 minutes at room temperature to obtain a slurry containing a white powdery composite. The obtained slurry was washed and dried in the same manner as in Example 1 to obtain a white reactant-4.

(Example 5)
(Method for producing a reaction product of 1,3-benzenedimethanol / potassium zirconium carbonate / orthophthalic acid chloride)
An organic solvent solution (1-1) was prepared in the same manner as in Example 4 except that 6.70 g of orthophthalic acid chloride was used as the aromatic dicarboxylic acid halide (a) and 4.56 g of 1,3-benzenedimethanol was used as the diol (c). 5) was obtained. A transparent and uniform aqueous solution (2-5) was obtained in the same manner as in Example 4 except that 21.3 g of zirconium carbonate aqueous solution Zirmel 1000 (Nihon Light Metal Co., Ltd.) was used as the metal compound (b-1). These two liquids were mixed in the same manner as in Example 4 to obtain a slurry containing a white powdery composite. This was washed and dried in the same manner as in Example 1 to obtain a white reaction product-5.

(Example 6)
(Method for producing a reaction product of ethylene glycol / clay mineral / isophthalic acid chloride)
The same organic solvent solution as that used in Example 4 was prepared as the organic solvent solution (1-6). Next, as an aqueous solution (2-6), synthetic hectorite (chemical formula Na _0.33 (Mg _2.67 Li _0.33 ) Si ₄ O ₁₀ (OH) ₂ : manufactured by Coop Chemical Co., Ltd. (Lucentite SWN ") 1.38 g and 2.84 g of sodium hydroxide were added and stirred at room temperature for 15 minutes to obtain a translucent homogeneous transparent aqueous solution. These two liquids were mixed in the same manner as in Example 4 to obtain a slurry containing a white powdery composite. This was subjected to the same washing and drying treatment as in Example 1 to obtain white reactant-6.

(Comparative example)
(Comparative Example 1: No metal compound (b-1) of Example 1)
The organic solvent solution (1) and the aqueous solution (2) are mixed in a stirring vessel having an anchor blade in the same manner as in Example 1 except that the aqueous solution (2) in Example 1 does not contain sodium aluminate powder. did. Unlike the case of Example 1, no solid product was obtained and the washing step could not be carried out, so that it could not be used for the subsequent measurement.

(Comparative Example 2: Examination of change of aromatic dicarboxylic acid halide (a) of Example 1 to aliphatic dicarboxylic acid halide)
In the same manner as in Example 1, except that 6.70 g of isophthalic acid chloride in the organic solvent solution (1) in Example 1 was changed to 6.10 g of adipoyl chloride, which is an aliphatic carboxylic acid dihalide, 1) and the aqueous solution (2) were mixed in a stirring vessel having an anchor blade. Unlike in the case of Example 1, a small amount of light yellow product was generated. The product settled as soon as stirring was stopped, suggesting a high specific gravity. This product was washed in the same manner as in Example 1.

Comparative Example 3 shows a production study example of an organic-inorganic composite when inorganic fine particles are directly melt-kneaded with polyethylene terephthalate, which is a representative semi-aromatic polyester.
(Comparative Example 3: Melt kneading of polyethylene terephthalate and inorganic fine particles)
Using a lab plast mill C type (Toyo Seiki Seisakusho Co., Ltd.), which is a resin melt kneading apparatus, a test was conducted to combine silica fine particles and polyethylene terephthalate resin by the melt kneading method under the following conditions. (Heating temperature 260 ° C., mixer rotation speed 150 rpm, kneading time 10 minutes, mixed specimen: polyethylene terephthalate resin 35 g, silica fine particles (Nippon Aerogel product number # 200, average primary particle size 12 nm) 15 g.) In this method, inorganic fine particles Introduction into the apparatus was difficult due to the scattering of inorganic fine particles, and a large increase in torque was observed during melt kneading, but a white product was obtained. Agglomerated silica was seen in part of the product.

The reactants obtained in the respective examples and comparative examples were measured by the following method.
(Measurement 1) Method for Measuring Content of Inorganic Compound The obtained reaction product was precisely dried (composite mass) after absolutely dried by hot air drying at 150 ° C. for 2 hours, and this was measured at 600 ° C. in air using a muffle furnace. After baking for 2 hours, the polymer component was completely burned off, and the mass after baking was measured to obtain the ash mass. The ash content was calculated from the following formula.

  In Examples 1 to 6 and Comparative Example 3, it was clarified that a certain amount burned out and was a composite of an organic component and an inorganic component. In Examples 1 to 6, it was suggested that the shape before firing was generally maintained after firing and was a uniform composite material, but in Comparative Example 3, the fired product was disjoint and did not remain in its original form. On the other hand, in Comparative Example 2, 90% by mass or more remained as the ash content, and it became clear that substantially no organic component was generated, that is, no polymer synthesis occurred. Accordingly, Comparative Example 2 was not evaluated thereafter.

(Measurement 2) Verification of inorganic components (measurement with fluorescent X-ray)
About 1 g of the obtained powder of the reaction product was set in a measurement holder having an opening having a diameter of 10 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 results of the obtained total element analysis, the sample data (powder, correction component; cellulose) of the measurement sample was given to the apparatus, and the element existence ratio in the complex was calculated.

  The reactants obtained in any of the examples are also derived from the metal compound (b-1) and the inorganic element derived from the alkali silicate (b-2) (in the case of sodium aluminate, aluminum, in the case of potassium zirconium carbonate, zirconium, silicic acid). Silicon was detected in the case of sodium (water glass), zinc was detected in the case of sodium zincate, and magnesium and silicon derived from synthetic hectorite were detected when the clay mineral (b-3) was used. Therefore, it was shown that the target inorganic compound was compounded in these examples, and also in Comparative Example 3, the inorganic component (silicon) corresponding to the fine particle silica of the inorganic raw material could be detected.

  On the other hand, only traces of the alkali metal element were detected in the reactants obtained in Examples 1-6. This is because the alkali metal compound in the metal compound (b-1), alkali silicate (b-2), and clay mineral (b-3) reacts with halogen (chlorine) in the monomer to give an alkali halide (NaCl, KCl). It is thought that this is because it was discharged out of the system during the cleaning process.

(Measurement 3) Verification of polymer components (Fliers conversion type infrared spectroscopic analysis: measurement of FT-IR)
A sample obtained by mixing and pulverizing the obtained powder of the reaction product 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, a very strong absorption peak was observed in a region showing an ester bond of 1700 cm ⁻¹ . In addition, a slight peak derived from the acid anhydride was observed at 1800 cm ⁻¹ . With respect to these peak intensity ratios, ester: acid anhydride = 95: 5 was obtained in each example.
The acid anhydride is expected to be derived from a side reaction in which an acid halide and an alkali metal ion component react to form C-ONa and then combine with another acid halide. However, since these amounts were very small, it was confirmed that the polyester as designed was produced by the method of the present invention.

(Measurement 4) Preparation of Sample for Transmission Electron Microscope (TEM) The obtained reaction product was hot-pressed for 2 hours under the conditions of 170 ° C. and 20 MPa to obtain a flake made of the reaction product having a thickness of about 1 mm. This was made into an ultrathin slice having a thickness of 75 nm using a focused ion beam apparatus. The obtained slices were observed for inorganic particle size and shape based on TEM photographs of 500,000 times each using “JEM-2010EFE” (manufactured by JEOL Ltd.) which is an energy filter TEM.
Similarly, the sample obtained in Comparative Example 3 was hot-pressed at 250 ° C. and 10 MPa for 2 minutes to obtain a flake made of a reaction product having a thickness of about 1 mm, and then the same method as in each Example. A sample for TEM was obtained.

(Measurement 5) Measurement of particle size of inorganic main component As for the particle size of the inorganic component, 100 particle sizes were measured from a TEM photograph, and the average value was defined as the average particle size. In addition, the measuring method of the particle size was performed as follows according to the particle shape.
(When the particles are substantially spherical): The length of an arbitrary side is defined as the particle size of the particles. When the inorganic component was silica, zirconium oxide, or zinc oxide, measurement was performed 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 or clay mineral, the measurement was performed by this method.

  Table 1 below summarizes the results of Examples 1 to 6 and the measurement results of Comparative Example 3.

As shown in Table 1, metal oxide (b-1), alkali silicate (b-2), clay while synthesizing semi-aromatic polyester by reacting aromatic dicarboxylic acid halide (a) and diol (c) An organic-inorganic composite could be produced by compositing inorganic components using an inorganic compound (B) selected from minerals (b-3) as a raw material. The resulting composite material had a sufficiently small inorganic particle size of 70 nm or less, and the inorganic content could be increased to 15 to 53%. Furthermore, various inorganic compounds could be compounded by changing the type of inorganic raw material.
On the other hand, Comparative Example 1 is an example in which the inorganic compound (B) that supplies the alkali component that accelerates the polycondensation reaction of the semiaromatic polyester does not exist in the system, but the polymerization reaction of the semiaromatic polyester hardly occurs. It was. Moreover, although the comparative example 2 is an example using only aliphatic dicarboxylic acid halide, the organic polymer was not produced | generated substantially. Comparative Example 3 is an example in which silica fine particles are melt-kneaded with polyethylene terephthalate resin, which is a semi-aromatic polyester. However, although fine particles having a primary particle size of 12 nm are used, aggregation cannot be unraveled and inorganic A dispersion having a small particle size was not obtained.

The organic-inorganic composite obtained in the present invention can be molded by a treatment such as a hot press and can be used as various structural materials. Further, the obtained organic-inorganic composite is melt-kneaded and added to other resins, particularly semi-aromatic polyesters such as PET having a similar structure, so that the strength of the inorganic components in the composite is increased with respect to the resin. Properties such as elastic modulus, impact resistance, electronic conductivity, antistatic properties, gas barrier properties and the like can be imparted.

Claims (4)

An organic solvent solution (1) containing an aromatic dicarboxylic acid halide (a);
A metal compound (b-1) having two or more metal elements containing at least one alkali metal selected from the group consisting of a metal oxide, a metal hydroxide and a metal carbonate, an alkali silicate (b-2), and An aqueous solution (2) containing at least one inorganic compound (B) selected from the group consisting of clay minerals (b-3);
In a state where the diol (c) is contained in one or both of the organic solvent solution (1) and the aqueous solution (2), the organic solvent solution (1) and the aqueous solution (2) are at least partially in phase. Production of an organic-inorganic composite, characterized in that the aromatic dicarboxylic acid halide (a) and the diol (c) react with each other while being kept in a dissolved state or in a separated state, and at the same time, an inorganic component is precipitated. Method. The method for producing an organic-inorganic composite according to claim 1, wherein the metal compound (b-1) is at least one selected from the group consisting of alkali aluminate, alkali stannate, alkali zincate, and alkali alkali carbonate. The method for producing an organic-inorganic composite according to claim 1 or 2, wherein an average particle size of the inorganic component is 5 nm to 100 nm. The organic-inorganic composite whose content rate of the inorganic component in 100 mass% obtained by the manufacturing method of the organic-inorganic composite in any one of Claims 1-3 is 10-60 mass%.