JPH11263876A - Organic-inorganic complex, hybrid material using the same and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic-inorganic complex which is prepared through an easy method without using special devices, etc., and a hybrid material which has various use such as mold materials, films, bottles, fibers, etc., has a strong interaction at the interface of a polymer matrix and an organic-inorganic complex which is a filler and provides sufficient mechanical properties. SOLUTION: This organic-inorbanic complex mainly comprises a lamellar compound. Between the layers of the lamellar compound, a metal cation which compensates the negative charge at the layer surface, at least one organic compound having at least one chemical bond chosen from a carbon-carbon double bond, a carbon-carbon triple bond, an ester bond, an amide bond and an ether bond and/or a functional group chosen from a hydroxyl group, a carboxyl group and an amino group and/or an atom chosen from a phosphorus atom and a nitrogen atom, and/or a polymer thereof coexist. A hybrid material is prepared by finely dispersing an organic-inorganic complex in a polymer matrix.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organic-inorganic composite, a hybrid material using the inorganic-organic composite, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, there has been known a method of adding an inorganic filler such as glass fiber, carbon fiber, calcium carbonate or clay mineral to improve the heat resistance and mechanical properties of a polymer. However, in many cases, the mutual force at the interface between the polymer and the inorganic filler is weak, and sufficient mechanical properties cannot be obtained, or the packing ratio must be increased in order to obtain sufficient mechanical properties. There was a problem that the specific gravity was increased.

In recent years, in order to solve this problem, a technique of dispersing montmorillonite, which has been organically treated with 12-aminododecanoic acid, in the order of nanometers in polyamide has been disclosed in Japanese Patent Application Laid-Open Nos. 62-74957 and 7-78089. Have been. However, this method has a problem in that although a remarkable improvement in mechanical properties and heat resistance is observed, a step of previously organizing montmorillonite with an amino acid or the like using a dispersion medium is required, and the process is complicated. was there.
Further, since an ion exchange reaction is used, the organic compound to be intercalated is limited to an ionic compound.

On the other hand, Japanese Patent Application Laid-Open No. Hei 6-248176 discloses a method in which swellable fluorine mica is used and highly dispersed in polyamide without performing an organic treatment. However, this method requires the use of a special polymerization method using high pressure, and lacks generality that can be applied to other resins.

[0005]

The present invention provides an organic-inorganic composite which can be produced by treating a layered compound by a simple method, and a hybrid material in which the organic-inorganic composite is highly dispersed in a polymer matrix. The purpose is to:

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and have found that a specific chemical bond,
An organic compound having a functional group and an atom and / or a polymer thereof are directly contacted with a layered compound without using a dispersion medium, and a specific organic compound is easily intercalated between layers by applying a shearing stress. Heading that
The present invention has been reached.

That is, the present invention has the following configuration. (1) It is mainly composed of a layered compound, and is selected from a metal cation for compensating a negative charge on a layer surface and a carbon-carbon double bond, a carbon-carbon triple bond, an ester bond, an amide bond, and an ether bond between layers of the layered compound. At least one of a chemical bond and / or a functional group selected from a hydroxyl group, a carboxyl group, and an amino group; a phosphorus atom and an atom selected from a nitrogen atom; An organic-inorganic composite, wherein an organic compound and / or a polymer thereof coexist. (2) The organic compound is at least one selected from the group consisting of acrylates, methacrylates, phosphonium salts, ammonium salts, phosphines, phosphine oxides, lactones, lactams, glycols, and polyethers. The organic-inorganic composite according to (1), which is an organic compound. (3) A hybrid material, wherein the organic-inorganic composite according to (1) or (2) is finely dispersed in a polymer matrix. (4) The polymer matrix is a polyacrylate, polyester, polyamide, polyesteramide,
The hybrid material according to (3), which is a polymer matrix comprising at least one of polyether, polyetherester, and polyetheresteramide. (5) A layered compound having a metal cation for compensating the negative charge on the layer surface between layers, a chemical bond selected from a carbon-carbon double bond, a carbon-carbon triple bond, an ester bond, an amide bond, and an ether bond, a hydroxyl group, and a carboxyl group , A functional group selected from an amino group, at least one chemical bond among atoms selected from a phosphorus atom and a nitrogen atom, and / or at least one organic compound having a functional group and / or an atom and / or a compound thereof. The organic compound according to (1) or (2), wherein the organic compound and / or a polymer thereof is intercalated between the layers of the layered compound by directly contacting the coalescing compound and applying a shearing stress. A method for producing an inorganic composite. (6) The hybrid according to (3) or (4), wherein the organic-inorganic composite according to (1) or (2) is polymerized to finely disperse the organic-inorganic composite in a polymer matrix. Material manufacturing method. (7) By adding the organic-inorganic composite according to (1) or (2) to a polymerization reaction system for forming a polymer matrix and polymerizing, the organic-inorganic composite is finely dispersed in the polymer matrix. A method for producing a hybrid material according to (3) or (4), wherein (8) The polymer constituting the polymer matrix and (1)
Alternatively, the method according to (3) or (4), wherein the organic-inorganic composite is finely dispersed in a polymer matrix by mixing with the organic-inorganic composite according to (2).

Hereinafter, the configuration of the present invention will be described in more detail.

The organic-inorganic composite of the present invention has a structure in which a positively charged metal ion for compensating the negative charge on the layer surface and a specific organic compound coexist between the layers of the negatively charged layered compound. . The organic compound coexisting with the metal ion is generally electrically neutral, but in the present invention, there is no problem even if it has a positive charge. In the organic-inorganic composite of the present invention, it is considered that the organic compound has some interaction with the metal ion and is intercalated between the layers by adsorption.

The organic-inorganic composite of the present invention is suitable for finely dispersing in a polymer matrix to form a hybrid material.

The layered compound used in the organic-inorganic composite of the present invention is not particularly limited as long as it has a layered structure and swells with water and / or an organic solvent, and is used as an inorganic filler. Such as clay minerals and mica, and these may be either natural products or synthetic products. Examples of the clay mineral include smectite-based clay minerals such as montmorillonite, saponite, hectorite, and stevensite. Examples of mica include muscovite, biotite, synthetic fluorine mica, and the like.

In order to compensate for the negative charge on the layer surface, the above layered compound contains lithium, sodium, calcium,
Contains metal cations such as copper and aluminum,
It is preferable that lithium ions and sodium ions are present between the layers, from the viewpoint of easy dispersion in the polymer matrix during formation of the hybrid material. As the layered compound, montmorillonite, saponite, and synthetic fluorine mica containing lithium ions and sodium ions between layers are particularly preferable.

In the organic-inorganic composite of the present invention,
The easiness of dispersion in the polymer matrix at the time of forming the hybrid material is governed by the interlayer bonding force of the layered compound and is estimated from the cation exchange capacity. In the present invention, the cation exchange capacity of the layered compound is 15 to 15.
It is preferably in the range of 150 meq / 100 g.
Those having 0 to 150 meq / 100 g are particularly preferred.

The shape and particle size of the layered compound are not particularly limited, and may be appropriately set according to the purpose of use such as the state of dispersion in the polymer matrix. A commonly used pulverization method such as a mixer, a visco mill, and a ball mill can be used to form a desired shape and size.

The specific organic compound and / or its polymer used in the organic-inorganic composite of the present invention is a chemical compound selected from a carbon-carbon double bond, a carbon-carbon triple bond, an ester bond, an amide bond and an ether bond. Bond, hydroxyl group, carboxyl group, functional group selected from amino group, phosphorus atom,
An organic compound having at least one kind of chemical bond and / or functional group and / or atom among atoms selected from nitrogen atoms and / or a polymer thereof, which may be used alone or as a mixture of two or more kinds. You may.

Preferred examples of the organic compound include acrylates, methacrylates, phosphonium salts, ammonium salts, phosphines, phosphine oxides, lactones, lactams, glycols, and polyethers.

Specific examples of acrylates and methacrylates include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, and diethylene glycol dimethacrylate. Acrylate, diethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, glycidyl acrylate,
Glycidyl methacrylate, acrylamide, methacrylamide and the like can be mentioned, and acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, acrylamide and methacrylamide are preferable from the viewpoint of ease of intercalation between layers of the layered compound.

Further, as a compound having a double bond, a vinyl monomer such as acrylonitrile or styrene can be added. Further, as a compound having a triple bond,
Alkynes such as acetylene, propyne, pentine, hexine and the like can be mentioned.

Examples of specific phosphonium salts include:
Examples thereof include tetrabutylphosphonium bromide, octyltributylphosphonium bromide, hexadecyltributylphosphonium bromide, vinylbenzyltriethylphosphonium chloride, and bis (hydroxypropyl) octadecylisobutylphosphonium chloride, with tetrabutylphosphonium bromide being particularly preferred.

Specific examples of ammonium salts include:
Examples thereof include tetraethylammonium salt, trimethyloctylammonium salt, ammonium salt of 6-amino-n-caproic acid, ammonium salt of 12-aminododecanoic acid, and choline chloride.

Specific examples of phosphines include trimethylphosphine, triethylphosphine, tri-n-
Examples thereof include butyl phosphine, tris-3-hydroxypropyl phosphine, and triphenyl phosphine, and particularly preferred is triphenyl phosphine.

Specific examples of phosphine oxides include trimethyl phosphine oxide, triethyl phosphine oxide, tributyl phosphine oxide, triphenyl phosphine oxide, and tris-3-hydroxypropyl phosphine oxide.
3-Hydroxypropylphosphine oxide is preferred.

Specific examples of lactones include β-propyl lactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, etc., and ε-caprolactone is particularly preferred.

Specific examples of lactams include δ-valerolactam, ε-caprolactam, ω-enantholactam, ω-laurinlactam and the like, with ε-caprolactam being particularly preferred.

Specific examples of glycols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,10-decanediol, and ethylene glycol is particularly preferred.

Specific examples of polyethers include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol having various molecular weights.

In the organic-inorganic composite of the present invention, the amount of the organic compound intercalated between the layers of the layered compound and / or the polymer thereof is 5 parts by weight or more based on 100 parts by weight of the layered compound. preferable. When the amount is less than 5 parts by weight, the amount of the organic compound and the polymer present between the layers is small, so that it is difficult to disperse in the polymer matrix at the time of forming the hybrid material, and the hybrid material has good dispersibility of the organic-inorganic composite. Can not be obtained.

Next, a method for producing the organic-inorganic composite of the present invention will be described. First, the above-mentioned layered compound is brought into direct contact with the above-mentioned organic compound and / or polymer thereof, but without using a dispersion medium. Therefore, shear stress is essential for intercalating the organic compound and / or its polymer between the layers of the layered compound, and by applying the shear stress, when the organic compound and / or its polymer is a liquid, the solid- The organic compound and / or the polymer is intercalated between the layers by a reaction between liquids or a solid-solid reaction when the organic compound and / or the polymer thereof is a solid. In the above reaction, as a device for applying a shear stress, a general stirring device such as a kneader, a Brabender, an extruder, a reaction vessel with a stirring device, or a mortar may be used.

As described above, a hybrid material can be formed using the organic-inorganic composite of the present invention.
The hybrid material of the present invention has a structure in which the above-mentioned organic-inorganic composite is finely dispersed in a polymer matrix.

The polymer matrix in the hybrid material of the present invention includes at least one of polyacrylate, polyester, polyamide, polyesteramide, polyether, polyetherester, polyetheresteramide and the like.

In the hybrid material of the present invention, the dispersion state of the organic-inorganic composite is not particularly limited, but it is preferable that the layered compound is further cleaved and dispersed in the polymer matrix from the viewpoint of mechanical properties and the like.

The hybrid material of the present invention may further contain other inorganic fillers, heat stabilizers,
There is no problem even if additives such as an antioxidant and a pigment are blended.

Next, a method for producing the hybrid material of the present invention will be described. As a method for producing this hybrid material, a method of polymerizing the organic-inorganic composite, or a method of adding and polymerizing the organic-inorganic composite to a polymerization reaction system for forming a polymer matrix, or a polymer constituting a polymer matrix A method of mixing with the organic-inorganic composite is mentioned.

When the organic compound and / or the polymer thereof intercalated between the layers of the layered compound has a double bond, the organic compound and / or the polymer itself has the ability to increase the molecular weight. A hybrid material can be produced by radical polymerization or emulsion polymerization of the organic compound and / or a polymer thereof. Even when the organic compound and / or its polymer is a lactone or a lactam, since the compound itself has the ability to increase the molecular weight, the hybrid material is produced by ring-opening polymerization of the organic compound and / or its polymer. Can be manufactured.

When the organic compound and / or the polymer thereof has a functional group such as a hydroxyl group, a carboxyl group or an amino group, the functional group has a reactivity with, for example, a carboxyl group or a hydroxyl group of a monomer. By adding the inorganic composite to a polycondensation reaction system such as polyester and polyamide, the organic compound and / or its polymer react to produce a hybrid material.

Further, even when the organic compound and / or the polymer thereof has no ability to increase the molecular weight and does not have a functional group having reactivity with the monomer, the organic compound and / or the polymer thereof may be used as a monomer. The organic-inorganic composite is mixed with the polymer constituting the polymer matrix, and dispersed by kneading or the like in order to impart swelling property due to the above or to impart a compatibilizing function such as showing an affinity with the polymer. Thus, a hybrid material can be manufactured.

The hybrid material of the present invention can be formed into molded articles, films, bottles, etc. by performing injection molding, press molding, blow molding and the like using a general molding apparatus.

Hereinafter, the present invention will be described more specifically with reference to Test Examples and Examples, but the present invention is not limited thereto. Test example Test Method (1) For the organic-inorganic composites of Examples 1 to 13 and Comparative Example 3, and the layered compounds of Comparative Examples 1 and 2, the interlayer distance of the layered compound in each material was measured using an X-point diffractometer RINT (40 KV-3).
7.5 mA, manufactured by Rigaku Corporation), and the angle dependence of the diffraction intensity was measured in the range of the scanning angle 2 ° or 3 ° ≦ 2θ ≦ 10 °. The interlayer distance was calculated from the angle corresponding to the obtained diffraction peak by Bragg's equation. (2) Regarding the films of Example 14 and Comparative Example 4 (1)
X-ray diffraction measurement was performed using the same apparatus as that described above.

2. Test Results (1) Table 1 shows the values of the obtained interlayer distances. From the results in Table 1, the organic-inorganic composites of Examples 1 to 13 have a larger interlayer distance than Comparative Examples 1 and 2, and the organic compound is an organic-inorganic composite in which an organic compound is intercalated between the layers. confirmed. On the other hand, in the organic-inorganic composite of Comparative Example 3, the interlayer distance was the same as in Comparative Examples 1 and 2, and it was found that the organic compound was not intercalated between the layers. (2) In the film of Example 14, disappearance of the diffraction peak derived from the laminated structure of the synthetic mica was observed, and it was confirmed that the film was a good hybrid material. On the other hand, in the film of Comparative Example 4, a diffraction peak derived from the laminated structure of the synthetic mica was observed, and it was confirmed that the film was not hybridized.

[0040]

EXAMPLES Examples 1 to 13 Organic-inorganic composites were produced in the combinations shown in Table 1 using the materials shown below. Drying the layered compound at 80 ° C. overnight,
0.5 part by weight of the organic compound was added to 1 part by weight of the layered compound, and the mixture was stirred in a mortar for 5 minutes to apply a shear stress to produce an organic-inorganic composite. Layered compound: Kunipia F (manufactured by Kunimine Industries Co., Ltd.) (cation exchange capacity: 115 meq / 100 g) Synthetic mica somasif ME-100 (manufactured by Corp Chemical Co.) (cation exchange capacity: 70-80 meq) / 100 g) Organic compound: • polyethylene glycol (# 600) • 1,4-butanediol • acrylamide • acrylic acid • hydroxyethyl acrylate • choline chloride • tri-n-butylphosphine • tetra-n-butylphosphonium bromide • tris- 3-hydroxypropylphosphine, tris-3-hydroxypropylphosphine oxide, ε-caprolactone, ε-caprolactam, ethylene glycol All reagent grades are used, and tetra-n-butylphosphonium bromide, tris-3-hydroxypropyl Sufin, tris-3-hydroxypropyl phosphine oxide was obtained from Nippon Chemical Industrial Corporation.

Example 14 1 part by weight of the organic-inorganic composite of Example 5, 5 parts by weight of hydroxyethyl acrylate, Irgacure 651 photoinitiator
(1% by weight based on hydroxyethyl acrylate) were mixed, and the mixture was sandwiched with a polyester film, and irradiated with a high-pressure mercury lamp (3 kW) from both sides for 10 minutes to obtain a film.

Comparative Examples 1 and 2 Layered compounds (Kunipia F, synthetic mica somasif ME-10)
No. 0) was stirred in a mortar for 5 minutes without adding an organic compound, and a shearing stress was applied thereto to obtain Comparative Examples 1 and 2.

Comparative Example 3 An organic-inorganic composite was produced in the same manner as in Example 3 except that hexamethylene diisocyanate was used instead of acrylamide in Example 3.

Comparative Example 4 A film was obtained in the same manner as in Example 14 except that only the synthetic mica Somasif ME-100 (manufactured by Corp Chemical Co.) was used instead of the organic-inorganic composite in Example 14.

[0045]

[Table 1]

[0046]

As described above, the organic-inorganic composite of the present invention can be produced by a simple method without using a special device or the like. The hybrid material of the present invention has a strong mutual force at the interface between the polymer matrix and the organic-inorganic composite as a filler by finely dispersing the organic-inorganic composite of the present invention in various polymer matrices. Characteristic is obtained. Therefore, the hybrid material of the present invention is useful for various uses such as molding materials, films, bottles, and fibers.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Nobuyuki Kinan 2-1-1 Katata, Otsu-shi, Shiga Prefecture Toyobo Co., Ltd. Research Institute (72) Inventor Hiroaki Taguchi 2-1-1 Katata, Otsu-shi, Shiga Prefecture Toyobo Co., Ltd.

Claims (8)

[Claims] Claims: 1. A metal cation mainly consisting of a layered compound, wherein a metal cation for compensating a negative charge on the layer surface and a carbon-carbon double bond, a carbon-carbon triple bond, an ester bond, an amide bond, or an ether bond are provided between the layers of the layered compound. Chemical bonds,
At least one organic compound having at least one chemical bond and / or a functional group and / or an atom selected from a functional group selected from a hydroxyl group, a carboxyl group, and an amino group, a phosphorus atom, and a nitrogen atom; And / or an organic-inorganic composite characterized by coexistence with a polymer thereof. 2. The method according to claim 1, wherein the organic compound is at least one selected from the group consisting of acrylates, methacrylates, phosphonium salts, ammonium salts, phosphines, phosphine oxides, lactones, lactams, glycols, and polyethers. 2. The organic-inorganic composite according to claim 1, which is a kind of organic compound. 3. A hybrid material wherein the organic-inorganic composite according to claim 1 or 2 is finely dispersed in a polymer matrix. 4. The polymer matrix according to claim 3, wherein the polymer matrix is at least one of polyacrylate, polyester, polyamide, polyesteramide, polyether, polyetherester, and polyetheresteramide. Hybrid material. 5. A layered compound having a metal cation for compensating negative charge on a layer surface between layers, a chemical bond selected from a carbon-carbon double bond, a carbon-carbon triple bond, an ester bond, an amide bond, an ether bond, a hydroxyl group, At least one organic compound having at least one chemical bond and / or a functional group and / or an atom selected from a functional group selected from a carboxyl group and an amino group, a phosphorus atom, and a nitrogen atom; and / or The organic compound according to claim 1 or 2, wherein the organic compound and / or the polymer is intercalated between layers of the layered compound by directly contacting the polymer and applying a shearing stress. A method for producing an inorganic composite. 6. The hybrid material according to claim 3, wherein the organic-inorganic composite is finely dispersed in a polymer matrix by polymerizing the organic-inorganic composite according to claim 1 or 2. Production method. 7. The method according to claim 1, wherein the organic-inorganic composite is finely dispersed in the polymer matrix by adding and polymerizing the organic-inorganic composite according to claim 1 to a polymerization reaction system for forming a polymer matrix. The method for producing a hybrid material according to claim 3 or 4, wherein: 8. A polymer constituting the polymer matrix and the organic-inorganic composite according to claim 1 or 2, whereby the organic-inorganic composite is finely dispersed in the polymer matrix. 3 or 4
A method for producing the hybrid material as described above.