JP3537957B2 - Clay composite material and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a clay composite material and a method for producing the same. More specifically, the present invention provides a novel seed material capable of dispersing clay minerals at a molecular level in rubber having low polarity.

[0002]

2. Description of the Related Art Conventionally, addition and mixing of clay minerals have been studied in order to improve the mechanical properties of rubber materials. For example, Japanese Patent Application Laid-Open No. 1-198645 discloses a method of organizing a clay mineral by using an oligomer having an onium ion introduced into a terminal or a side chain, and mixing the clay mineral into a rubber material. .

[0003]

However, in the above-mentioned conventional clay composite rubber material, it is not always easy to prepare an oligomer into which onium ions are introduced. In addition, the swelling between the clay layers was sometimes insufficient because the oligomer was immediately introduced into the clay layers. Also,
According to Giannelis et al., When polystyrene having no polar group is used, one polystyrene molecule is present between the layers.
Only layers can enter, and interlayer swelling is limited (EP Giannelis et al., Chem. Mate.
r. 5,1694-1696 (1993)).

[0004] The inventors of the present application have developed a technique for allowing an oligomer or polymer having a polar group in a molecule to sufficiently penetrate between layers of a clay mineral that has been organically treated by onium ions, A technique for introducing an oligomer or polymer having no polar group between the clay layers after introducing a low molecular substance having a polar group between the layers has already been filed (“Clay composite material and its production method”, June 1995). Filed on March 5, “Clay composite material and its manufacturing method,
As well as blend materials ”filed on June 30, 1995). However, when guest molecules such as oligomers are mixed with rubber,
The viscosity before unvulcanization decreased, and the elastic modulus sometimes slightly decreased during vulcanization.

In view of the above problems, the present invention provides a clay composite material capable of uniformly dispersing a clay mineral at a molecular level in a polymer and having excellent mechanical strength and creep resistance, and a method for producing the same. What you are trying to do.

[0006]

According to the first aspect of the present invention, there is provided a clay mineral organically formed by ionic bonding of an organic onium ion having an unsaturated carbon chain having 6 or more carbon atoms, a clay mineral having a polar group in the molecule, A guest molecule having an unsaturated carbon chain whose length is equal to or larger than that of the organic onium ion, and a cross-linking agent capable of forming a cross-link between the unsaturated bond of the organic onium ion and the unsaturated bond of the guest molecule The organic onium ion and at least a part of the guest molecule enter between the layers of the clay mineral, and a hydrogen bond is formed between the clay mineral and a polar group of the guest molecule. It is a clay composite material characterized by having been done.

The most remarkable feature of the present invention is that the clay mineral is organically formed by forming an ionic bond between the clay mineral and an organic onium ion having an unsaturated carbon chain. To form a cross-link between the ion and the guest molecule.

The operation and effect of the present invention will be described. In the clay composite material of the present invention, as described above, the clay mineral is organized by forming an ionic bond with the organic onium ion. Organized clay minerals can provide a lot of space spatially. For this reason, the guest molecules can easily enter the interlayer of the clay mineral.

On the other hand, non-polar molecules can be once taken in between the layers of the clay mineral, but are often excluded by the polarity of the silicate layer. However, in the present invention, a guest molecule in which a non-polar molecule is provided with a polar group is incorporated between layers of the clay mineral. Therefore, the guest molecules that have entered between the layers of the clay mineral form hydrogen bonds between the unsaturated groups and the silicate layer of the clay mineral. For this reason, even if the guest molecule has a nonpolar portion, the guest molecule can stay between the layers by a hydrogen bond in which the unsaturated group is stably formed with the clay mineral.

As described above, even if it is difficult to swell the clay mineral by the present invention, it is possible to introduce at least one polar group into the guest molecule.
Can stay between layers of clay minerals. For this reason, it becomes possible to infinitely swell between the layers of the clay mineral more than the conventional limited swelling layer.

In the clay composite material of the present invention,
As described above, since the clay mineral is in an infinite swelling state, its surface area is significantly increased as compared with the conventional limited swelling. Therefore, it has a high barrier property against gas or liquid (water, oil, etc.). The behavior of guest molecules is restricted by the presence of clay minerals. For this reason, the entanglement of the guest molecular chains is less likely to be loosened. Therefore, mechanical strength such as tensile strength and elastic modulus of the member is increased. Also, the creep resistance is improved.

As an organic onium ion for organically converting a clay mineral, an ammonium salt of an alkylamine has conventionally been often used. However, the alkylamine has no unsaturated bond and has no site to react with the oligomer. Therefore, the alkylamine only acted as a plasticizer in the rubber. Therefore, in the present invention, a guest molecule having an unsaturated carbon chain is used as the guest molecule, and an organic onium ion having an unsaturated carbon chain is used as the organic onium ion. In addition, a cross-linking agent capable of binding unsaturated bonds of guest molecules is added to the clay composite material. Therefore, a cross-link is formed between the unsaturated bond of the guest molecule and the unsaturated bond of the organic onium ion. This cross-linking restricts the movement of rubber molecules near the silicate layer of the clay mineral, and has a favorable effect on the mechanical properties of the clay composite rubber material.

Next, details of the clay composite material of the present invention will be described. The clay composite material is composed of a clay mineral, an organic onium ion for organizing the clay mineral, a guest molecule penetrating between layers of the clay mineral, and a crosslinking agent for forming a crosslink between the organic onium ion and the guest molecule. Become.

It is preferable to use a clay mineral having a large contact area with a guest molecule. Thereby, the interlayer of the clay mineral can be largely swollen. Specifically, the cation exchange capacity of the clay mineral is preferably 50 to 200 milliequivalents / 100 g. If the amount is less than 50 milliequivalents / 100 g, onium ions may not be sufficiently exchanged, and it may be difficult to swell between layers of the clay mineral. On the other hand, if it exceeds 200 milliequivalents / 100 g, the bonding strength between the layers of the clay mineral becomes strong, and it may be difficult to swell the layers.

Examples of the clay mineral include montmorillonite, saponite, hectorite, beidellite,
There are smectite-based clay minerals such as stevensite and nontronite, vermiculite, halloysite, and swellable mica, which may be natural or synthesized.

Next, the organic onium ion has an unsaturated carbon chain having 6 or more carbon atoms. When the number of carbon atoms is less than 6, the hydrophilicity of the organic onium ion increases, and the compatibility with the guest molecule decreases. Examples of the organic onium ion include an alkenylamine ammonium salt. Alkenylamines include, for example,
1-hexenylamine, 1-dodecenylamine, 9-octadecenylamine (oleylamine), 9,12-octadecadienylamine (linolamine), 9.1
Examples thereof include 2,15-octadecatrienylamine and linoleylamine (linoleylamine).

Next, the guest molecule has a polar group in the molecule. The polar group is a group in which electrons are localized in the molecule of the guest molecule and a charge is biased, and does not include a completely polarized ion. Therefore, onium ions are not included in the polar groups.

The polar group of the guest molecule may be a hydroxyl group (OH), a halogen group (F, Cl,
Br, I), carboxyl group (COOH), carboxyl anhydride group (—COO—CO—), thiol group (SH),
One or two or more selected from the group of an epoxy group and an amino group (NH ₂ ).

The guest molecule has a molecular length equal to or larger than that of the organic onium ion. When the molecular length of the guest molecule is smaller than the molecular length of the organic onium ion, the guest molecule may not project outside the region where the organic onium ion exists at the interface of the clay mineral.
Therefore, the clay mineral may not be easily dispersed in a matrix such as a rubber material.

The guest molecule has an unsaturated carbon chain having an unsaturated bond in the molecule. The unsaturated bond is highly reactive and forms a cross-link with the unsaturated bond of the organic onium ion in the presence of the cross-linking agent.

The guest molecules are preferably oligomers or polymers having a molecular weight of 1,000 to 100,000. Molecular weight 100
If it is less than 0, the swelling between layers of the clay mineral may be insufficient. On the other hand, when the molecular weight exceeds 100,000, the guest molecule may be hardly soluble in the solvent, or the softening point or melting point may be higher than the decomposition point of the clay mineral.

The guest molecules at least partially penetrate between layers of the clay mineral. Not all guest molecules need to enter between the layers of the clay mineral. For example, if 10% by weight or more of the total amount of guest molecules enters, the interlayer swells sufficiently. If the amount is less than 10% by weight, swelling between layers of the clay mineral may be insufficient.

Next, the crosslinking agent forms a crosslinking bond from the unsaturated bond of the organic onium ion and the unsaturated bond of the guest molecule. As the cross-linking agent, any one can be used as long as it is used for cross-linking of rubber. In particular, as in the invention of claim 4, one or more kinds selected from the group consisting of sulfur, peroxide and phenolic resin are used. Preferably. The reason is that the above-mentioned cross-linking agent is most suitable as a cross-linking agent for rubber and can form the above-mentioned cross-linking most effectively.

Next, the clay composite material is preferably kneaded with a rubber material. As a result, the clay mineral can be uniformly dispersed with a large interlayer distance even in a rubber material in which the clay mineral has conventionally been difficult to disperse. Also, the unsaturated groups of the guest molecules co-vulcanize with the rubber. Therefore, a crosslink is formed in the ternary system of the guest molecule, the rubber, and the organic onium ion, and a clay composite rubber material having more excellent properties can be provided.

The rubber material is, for example, a guest molecule,
The same kind or different kinds may be used. Such rubber materials include, but are not limited to, butyl rubber, butadiene rubber, ethylene-propylene-diene rubber, natural rubber, polyisoprene, and the like. When the rubber material is different from the guest molecule, it is more desirable that the interlayer distance between the clay minerals is further increased. This is to uniformly disperse the clay mineral in the rubber material.

Next, a fifth aspect of the present invention provides a method for forming a clay mineral between the clay mineral and the organic onium ion by forming an organic onium ion having an unsaturated carbon chain having 6 or more carbon atoms into an ionic bond. The clay mineral is organically formed by forming an ionic bond, and then the clay mineral is converted into a guest having a polar group in the molecule and an unsaturated carbon chain having a molecular length equal to or larger than that of the organic onium ion. Contacting at least a part of the guest molecules between the layers of the clay mineral to form a hydrogen bond between the clay mineral and a polar group of the guest molecule; By mixing the onium ion and the guest molecule with a crosslinking agent, a crosslinking bond is formed between the unsaturated bond of the organic onium ion and the unsaturated bond of the guest molecule. A method for producing a clay composite material characterized in that to produce a clay composite material for kneading the rubber material.

The present invention is a method for producing a clay composite material for kneading a rubber material. The most notable aspects of this production method are that the organic onium ion, which is the organic agent of the clay mineral, has an unsaturated carbon chain, that the guest molecules penetrating between layers of the clay mineral have an unsaturated carbon chain, To form a crosslink between the carbon chain and the unsaturated carbon chain.

Next, the operation and effect of the method for producing the clay composite material will be described. In this manufacturing method, first, an organic onium ion is ion-bonded to the clay mineral to thereby make the clay mineral organic. This creates a sufficient space between the layers of the clay mineral for the guest molecules to enter.

Therefore, when guest molecules are brought into contact with the organic clay mineral, the guest molecules easily enter the spaces between the layers. Since the guest molecule has a polar group, the guest molecule forms a hydrogen bond with the clay mineral and stays between the layers of the clay mineral to make the interlayer of the clay mineral hydrophobic. Therefore, guest molecules of low polarity that penetrate into the layers of the clay mineral
It stays between layers without being excluded by the polarity of the clay mineral.

The guest molecule has a molecular length equal to or larger than that of the organic onium ion and is bulky. Therefore, the guest molecules stay between the layers, and the layers are infinitely swelled infinitely. Therefore, by kneading the clay composite material in an infinitely swelling state into a rubber material, the clay mineral, which is originally a polar substance, can be uniformly dispersed at a molecular level in a rubber material having a low polarity.

As described above, since the clay mineral is in an infinitely swollen state, its surface area is increased, and the clay mineral has high barrier properties against gas or liquid (water, oil, etc.). In addition, the behavior of the guest molecule is restricted by the presence of the clay mineral.
For this reason, the entanglement of the guest molecular chains is less likely to be loosened. Therefore, mechanical strength such as tensile strength and elastic modulus of the member is increased. Also, the creep resistance is improved.

The guest molecule has an unsaturated carbon chain,
Organic onium ions have an unsaturated carbon chain. Therefore, when the organic onium ion and the guest molecule are kneaded with the rubber material, a cross-link is formed in the ternary system of the rubber material, the organic onium ion, and the guest molecule in the presence of the cross-linking agent. As described above, the mechanical properties of the rubber material can be improved by the clay mineral being in an infinite swelling state and forming a ternary crosslinking bond in the rubber material.

Next, details of the method for producing the clay composite material will be described. As a method of bringing the clay mineral into contact with the organic onium ion, for example, there is an ion exchange method.
This ion exchange method is, for example, a method of immersing a clay mineral in an aqueous solution containing an organic onium ion and then washing the clay mineral with water to remove excess organic onium ion.

As a method of bringing guest molecules into contact with the organic clay mineral, for example, the guest molecules are swollen in a solvent, the guest molecules in the swollen state are brought into contact with the clay mineral, and then excess solvent is removed. There is a method of removing, and a method of bringing the guest molecule into contact with the clay mineral in a state of being softened or melted by heat.

According to the former method, guest molecules can be inserted between layers of the clay mineral at room temperature. Solvents that can be used in this method include, for example, non-polar solvents such as toluene, benzene, xylene, hexane, and octane.

In the latter method, when the guest molecules are softened or melted, the guest molecules are heated to a temperature equal to or higher than the softening temperature or the melting temperature. This heating does not decompose guest molecules and clay minerals,
It is carried out at a temperature that is stable. For example, the heating temperature is preferably 250 ° C. or less. If the temperature exceeds 250 ° C., the organized clay mineral may be decomposed. Other aspects of the method for producing the clay composite material are the same as those of the clay composite material.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiment 1 A clay composite material according to an embodiment of the present invention will be described with reference to FIG. As shown in FIG. 1, the clay composite material of this embodiment is a method of forming a clay mineral 7 organized by an organic onium ion 6 and a guest molecule 3 which is an unsaturated carbon chain having a polar group 30 in a molecule. It is kneaded in the presence. Between the layers of the clay mineral 7, organic onium ions 6
And a part of the guest molecule 3 enters.

Clay mineral 7 is sodium-type montmorillonite (produced in Yamagata Prefecture, ion exchange capacity 120 meq / 100).
g). The organic onium ion 6 is an oleyl ammonium ion, which has 18 carbon atoms and has one double bond in the molecule. The guest molecule 3 is polyisoprene having a hydroxyl group (manufactured by Kuraray: LIR506), and has a molecular weight of about 25,000. Guest molecule 3
Is equal to or larger than the molecular length of the organic onium ion 6. In addition, sulfur is used as a crosslinking agent.

Next, a method for producing the above-mentioned clay composite material will be described. First, add 20.0 g of montmorillonite to 80
Dispersed in 2000 ml of water at ℃. Next, 8.8 g of oleylamine hydrochloride was dissolved in 1500 ml of water at 80 ° C. Both of these aqueous solutions were mixed at once to produce a precipitate. The precipitate was washed twice with water at 80 ° C. to obtain montmorillonite organically treated with oleyl ammonium ion. This is called OL-montmorillonite. The inorganic content in OL-montmorillonite determined by the burning method was 69.4% by weight. When the interlayer distance of montmorillonite was measured by the X-ray diffraction method, the interlayer distance of OL-montmorillonite was 22.5 °.

Next, OL-montmorillonite 100 g
, 100 g of LIR506 was added and mixed at 80 ° C. for 4 hours. When the interlayer distance of montmorillonite in the clay composite material was measured by the X-ray diffraction method,
Met.

Next, 3.0 g of sulfur was added to the mixture.
(Crosslinking agent), zinc white 5.0 g, stearic acid 3.0 g,
Vulcanization accelerator (Noxeller MS manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)
AG) was added and kneaded to obtain a clay composite material as a seed material for natural rubber. This kind of material was added to and kneaded with natural rubber to obtain a clay composite rubber material.

Next, the operation and effect of this embodiment will be described. In the clay composite material of the present embodiment, as shown in FIG. 1, the clay mineral 7 is uniformly dispersed in the rubber molecules 9 by the organic onium ions 6 and the guest molecules 3 entering between the layers of the clay mineral 7. Further, a cross-link 11 is formed between the unsaturated bond of the guest molecule 3 and the unsaturated bond of the organic onium ion 6 in the seed material. Further, a cross-link 12 is formed between the unsaturated bond of the guest molecule 3 and the rubber molecule 9. As a result, the movement of rubber molecules near the silicate layer of the clay mineral is restricted, and the mechanical properties of the clay composite rubber material are favorably affected.

Second Embodiment The clay composite material of the first embodiment is different from the first embodiment in that a 1,2-polybutadiene oligomer is used as a guest molecule.
Is different from In producing the clay composite material of the present example, the OL-montmorillonite and the 1,2-polybutadiene oligomer (manufactured by Nippon Soda:
G3000) was mixed in 100 g portions. The interlayer distance of OL-montmorillonite (organized clay mineral) is 6
7.0 °.

Next, 3.0 g of sulfur was added to the mixture.
(Crosslinking agent), zinc white 5.0 g, stearic acid 3.0 g,
Vulcanization accelerator (Noxeller TT manufactured by Ouchi Shinko Chemical Co., Ltd.)
P) 1.5 g was added and kneaded to prepare a clay composite material as a seed material for butadiene rubber.

This seed material was added to butadiene rubber and kneaded to obtain a clay composite rubber material. The same effect as that of the first embodiment can be obtained also in the clay composite material of the present embodiment.

Embodiment 3 The clay composite material of this embodiment uses 1- as an organic onium ion.
The difference from the first embodiment is that dodecenylamine is used. In manufacturing the clay composite material of this example,
Using 6.4 g of 1-dodecenylamine hydrochloride instead of the oleylamine hydrochloride in Embodiment Example 1,
Montmorillonite was made organic. This organized montmorillonite is referred to as DO-montmorillonite.

Next, the above-mentioned DO-montmorillonite and 1,
100 g of 4-polybutadiene oligomer hydrogenated product (manufactured by Mitsubishi Chemical Corporation: Polytail H) was mixed. The interlayer distance of DO-montmorillonite (organized clay mineral) is 6
7.0 °.

Next, in the clay composite material, sulfur 3.
0 g (crosslinking agent), zinc white 5.0 g, stearic acid 3.0
g, 1.5 g of a vulcanization accelerator (NOCSELA MSA-G manufactured by Ouchi Shinko Chemical Co., Ltd.) was added and kneaded to prepare a butyl rubber seed material (clay composite material).

The seed material for butyl rubber was kneaded with a rubber material to obtain a clay composite rubber material. The same effect as that of the first embodiment can be obtained also in the clay composite material of the present embodiment.

[0050]

According to the present invention, it is possible to provide a clay composite material capable of uniformly dispersing a clay mineral at a molecular level in a polymer, and having excellent mechanical strength and creep resistance, and a method for producing the same. it can.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of a clay composite rubber material according to a first embodiment.

[Explanation of symbols]

11,12. . . Cross-linking, 3. . . Guest molecule, 30. . . Polar groups, 6. . . Organic onium ion, 7. . . Clay minerals, 9. . . Rubber molecule,

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Akane Okada 41 No. 41, Yokomichi, Yokomichi, Nagakute-cho, Aichi-gun, Aichi Prefecture Inside Toyota Central R & D Laboratories Co., Ltd. Address: Japan Denso Co., Ltd. (72) Inventor Isamu Inai 1-1-1, Showa-cho, Kariya, Aichi Prefecture Japan Denso Co., Ltd. (56) References JP-A-8-333114 (JP, A) JP-A-58-67338 (JP, A) JP-A-3-115114 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C01B 33/20-39/54 JTPPlus (JOIS)

Claims (5)

(57) [Claims] 1. A clay mineral organically formed by ionic bonding of an organic onium ion having an unsaturated carbon chain having 6 or more carbon atoms, a clay mineral having a polar group in the molecule, and the same molecular length as the organic onium ion. And a cross-linking agent capable of forming a cross-link between the unsaturated bond of the organic onium ion and the unsaturated bond of the guest molecule. The organic onium ion and at least a part of the guest molecule enter between the layers, and a hydrogen bond is formed between the clay mineral and a polar group of the guest molecule. Clay composite material. 2. The guest group according to claim 1, wherein the polar group of the guest molecule is a hydroxyl group (OH), a halogen group (F, Cl, B
r, I), one or more selected from the group consisting of a carboxyl group (COOH), a carboxyl anhydride group (—COO—CO—), a thiol group (SH), an epoxy group, and an amino group (NH ₂ ). Clay composite material characterized by the following. 3. The method according to claim 1, wherein the guest molecule is
A clay composite material comprising a oligomer or a polymer having a molecular weight of 1,000 to 100,000. 4. The clay composite material according to claim 1, wherein said cross-linking agent comprises one or more selected from the group consisting of sulfur, peroxide and phenolic resin. 5. The clay mineral, wherein an organic onium ion having an unsaturated carbon chain having 6 or more carbon atoms forms an ionic bond with the clay mineral to form an ionic bond between the clay mineral and the organic onium ion. Organizing the mineral and then contacting the clay mineral with a guest molecule having an unsaturated carbon chain with a polar group in the molecule and a molecular length equal to or greater than the organic onium ion At least a part of the guest molecule is inserted between the layers of the clay mineral to form a hydrogen bond between the clay mineral and a polar group of the guest molecule, and then the organic onium ion and the guest molecule are cross-linked. To form a cross-link between the unsaturated bond of the organic onium ion and the unsaturated bond of the guest molecule by mixing with the agent, and knead the rubber material. A method for producing a clay composite material, characterized by producing the clay composite material according to (1).