JP2001302888A - Phyllosilicate-reinforced olefin metathetic polymer and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a phyllosilicate-reinforced olefin metathetic polymer having various performances such as excellent mechanical properties, dimensional stability, heat resistance, flame retardance and gas barrier properties and to provide a method for efficiently and readily producing the polymer. SOLUTION: This phyllosilicate-reinforced olefin metathetic polymer is characterized as comprising an olefin metathetic polymer obtained by polymerizing an olefin metathetic reactive monomer using a metathetic polymerization catalyst and a phyllosilicate. The method for producing the phyllosilicate-reinforced olefin metathetic polymer is characterized by dispersing and mixing the phyllosilicate in the olefin metathetic reactive monomer and polymerizing the resultant mixture liquid in the presence of the metathetic polymerization catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a layered silicate-reinforced olefin metathesis polymer and a method for producing the same.
More specifically, the present invention relates to a layered silicate-reinforced olefin metathesis polymer having excellent mechanical properties, dimensional stability, heat resistance, flame retardancy, gas barrier properties, and the like, and a method for producing the same.

[0002]

2. Description of the Related Art It has been known that an olefin metathesis-reactive monomer forms an olefin metathesis polymer by a metathesis polymerization reaction. For example,
A method has been proposed in which an inexpensively obtained metathesis-polymerizable cyclic olefin such as dicyclopentadiene (DCPD) is polymerized and molded in one step in a mold in the presence of a metathesis polymerization catalyst to obtain a polymer molded product ( For example, JP-A-58-129003. According to such a method, a large-sized molded body can be obtained using an inexpensive low-pressure mold, and the obtained molded body has an excellent balance between mechanical properties such as rigidity and impact resistance. It can be used as a useful molded body.

However, depending on the application, higher mechanical properties, dimensional stability, heat resistance, flame retardancy, gas barrier properties, and the like are required, and various efforts have been made to satisfy such requirements. For example, JP-A-2-6525 discloses a reinforcing method for improving the strength, elastic modulus, heat resistance and the like of a molded product by dispersing glass fibers in an olefin metathesis polymer.

However, in the case of the above method, it is difficult to obtain a sufficient reinforcing effect only with short glass fibers, so that it is necessary to combine with short glass fibers, glass cloth, or the like. In the molding method of pouring into a mold such as, voids remain in the obtained molded body,
There are problems that the dimensions vary, and that the heat resistance of the molded body is not always sufficient.

[0005] Further, since the olefin metathesis polymer is an amorphous three-dimensional crosslinked polymer, there is a problem that the gas barrier property is inferior to a crystalline polymer such as a polyethylene resin or a polypropylene resin.

[0006] Further, olefin metathesis polymers include:
Generally, since the resin is a highly flammable resin, it is necessary to add a flame retardant, for example, in order to develop the flame retardancy. As the above-mentioned flame retardant, a halogen-containing flame retardant is generally used because a decrease in moldability and a decrease in mechanical strength of a molded article are relatively small. However, an olefin metathesis polymer containing a halogen-containing flame retardant may generate a large amount of halogen-based gas during molding or combustion, and the generated halogen-based gas may corrode equipment or damage human bodies. Since there is an unfavorable effect, there is a strong demand for a so-called non-halogen flame retardant treatment technique that does not use a halogen-containing flame retardant from the viewpoint of safety.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide excellent mechanical properties, dimensional stability,
An object of the present invention is to provide a layered silicate-reinforced olefin metathesis polymer having various properties such as heat resistance, flame retardancy and gas barrier properties, and an efficient and easy method for producing the same.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, they have found that the above object can be achieved by strengthening the olefin metathesis polymer with a layered silicate. Thus, the present invention has been completed. That is, the present invention provides a layered silicate-reinforced olefin metathesis polymer described in detail below and a method for producing the same.

The layered silicate-reinforced olefin metathesis polymer according to the first aspect of the present invention comprises a layered silicate and an olefin metathesis polymer obtained by polymerizing an olefin metathesis reactive monomer with a metathesis polymerization catalyst. It is characterized by becoming.

[0010] The layered silicate-reinforced olefin metathesis polymer according to the second aspect of the present invention is the layered silicate-reinforced olefin metathesis polymer according to the first aspect, wherein the amount of the layered silicate is 100 parts by weight of the olefin metathesis polymer. The blending amount is 0.1 to 100 parts by weight.

The layered silicate-reinforced olefin metathesis polymer according to the invention of claim 3 is the layered silicate-reinforced olefin metathesis polymer according to claim 1 or 2, wherein the olefin metathesis reactive monomer is norbornene. It is a monomer and / or a monocyclic cycloolefin.

According to a fourth aspect of the present invention, there is provided the layered silicate-reinforced olefin metathesis polymer according to the third aspect, wherein the norbornene-based monomer is dicyclopentadiene or dicyclopentadiene. It is at least one kind of norbornene-based monomer selected from the group consisting of derivatives, norbornene, ethylidene norbornene, and norbornadiene.

[0013] The layered silicate-reinforced olefin metathesis polymer according to the invention according to claim 5 is the layered silicate-reinforced olefin metathesis polymer according to claim 3, wherein the monocyclic cycloolefin is cyclooctadiene. It is characterized by.

The layered silicate-reinforced olefin metathesis polymer according to the invention of claim 6 is the same as the layered silicate-reinforced olefin metathesis polymer according to any one of claims 1 to 5, but is not limited to the olefin metathesis-reactive monomer. It is characterized in that 0.5 to 100 parts by weight of at least one flame retardant selected from the group consisting of a phosphorus compound, a metal hydroxide and a melamine derivative is added to 100 parts by weight.

The layered silicate-reinforced olefin metathesis polymer according to the invention according to claim 7 is the layered silicate-reinforced olefin metathesis polymer according to any one of claims 1 to 6, wherein the metathesis polymerization catalyst is It is a ruthenium-based complex.

The layered silicate-reinforced olefin metathesis polymer according to the invention of claim 8 is the layered silicate-reinforced olefin metathesis polymer of claim 7, wherein the ruthenium-based complex is represented by the general formula (1) It is characterized by being at least one ruthenium-based complex represented by the general formula (4).

The layered silicate-reinforced olefin metathesis polymer according to the ninth aspect of the present invention is the layered silicate-reinforced olefin metathesis polymer according to any one of the first to eighth aspects, wherein the layered silicate comprises: It is characterized by being montmorillonite and / or swellable mica.

The layered silicate-reinforced olefin metathesis polymer according to the invention according to claim 10 is the layered silicate-reinforced olefin metathesis polymer according to any one of claims 1 to 9, wherein the layered silicate comprises: It is characterized in that it is a layered silicate obtained by ion-exchanging exchangeable metal cations contained in the crystal structure with a cationic surfactant to make it organic.

The layered silicate-reinforced olefin metathesis polymer according to the invention of claim 11 is the layered silicate-reinforced olefin metathesis polymer according to any one of claims 1 to 10, wherein the layered silicate comprises: It is a layered silicate containing an alkylammonium ion having 6 or more carbon atoms.

The layered silicate-reinforced olefin metathesis polymer according to the invention of claim 12 is the layered silicate-reinforced olefin metathesis polymer according to any one of claims 1 to 11, wherein the layered silicate comprises: The layered silicate is characterized in that the average interlayer distance of the (001) plane measured by a wide-angle X-ray diffraction measurement method is 3 nm or more, and a part or all of the layered silicate is dispersed in five layers or less.

The layered silicate-reinforced olefin metathesis polymer according to the invention of claim 13 is the same as the layered silicate-reinforced olefin metathesis polymer of any one of claims 1 to 12, but having a power of 50 kW / m ² . Heating under radiation heating conditions for 30 minutes (ASTM E1354
The combustion residue burned in accordance with
The yield point stress when compressed at s is not less than 4.9 kPa.

The method for producing a layered silicate-reinforced olefin metathesis polymer according to the invention of claim 14 is the method for producing a layered silicate-reinforced olefin metathesis polymer according to any one of claims 1 to 13. The method
The layered silicate is dispersed and mixed in an olefin metathesis reactive monomer, and the resulting mixture is polymerized in the presence of a metathesis polymerization catalyst.

Further, the method for producing a layered silicate-reinforced olefin metathesis polymer according to the invention according to claim 15 is a method for producing the layered silicate-reinforced olefin metathesis polymer according to any one of claims 1 to 13. A method, wherein a metathesis polymerization catalyst is inserted (intercalated) into a layered silicate, and the obtained metathesis polymerization catalyst-inserted layered silicate is dispersed and mixed in an olefin metathesis reactive monomer and polymerized. .

The layered silicate-reinforced olefin metathesis polymer of the present invention contains an olefin metathesis polymer obtained by polymerizing an olefin metathesis-reactive monomer with a metathesis polymerization catalyst and a layered silicate.

The olefin metathesis reaction referred to in the present invention is not particularly limited, but typically means a reaction in which an alkylidene group of an olefin is exchanged as represented by the following reaction formula. R ¹ CH = CHR ¹ + R ² CH = CHR ² ⇔2R ¹ CH
ＣＨCHR ^{2 where} R ¹ CH ＝ CHR ¹ and R ² CH ＝ CHR
² represents an olefin metathesis reactive monomer, respectively)

The olefin metathesis reactive monomer used in the present invention is not particularly limited. For example, unsaturated olefins having at least one unsaturated double bond such as propylene and butadiene are used. An unsaturated cyclic olefin having at least one unsaturated double bond, such as cyclooctene, cyclooctadiene, norbornene, etc., which is preferably used. These olefin metathesis reactive monomers are:
They may be used alone or in combination of two or more.

Among the above-mentioned olefin metathesis reactive monomers, norbornene monomers are more preferably used because of their excellent metathesis reactivity and excellent mechanical properties such as rigidity of the resulting olefin metathesis polymer. Further, monocyclic cycloolefins are more preferably used because the obtained olefin metathesis polymer has excellent physical properties such as flexibility. The norbornene-based monomer and the monocyclic cycloolefin may be used alone or in combination.

The norbornene-based monomer is not particularly restricted but includes, for example, norbornene,
Bicyclics such as ethylidene norbornene and norbornadiene; tricyclics such as dicyclopentadiene and dihydrodicyclopentadiene; tetracyclics such as tetracyclododecene, ethylidenetetracyclododecene and phenyltetracyclododecene; tricyclopentadiene and the like A pentacyclic ring; a heptacyclic ring such as tetracyclopentadiene, and alkyl-substituted (eg, methyl, ethyl, propyl, butyl-substituted), alkylidene-substituted (eg, ethylidene-substituted), aryl-substituted (Eg, phenyl and tolyl-substituted products) and derivatives thereof having polar groups such as epoxy group, methacryl group, hydroxyl group, amino group, carboxyl group, cyano group, halogen group, ether group, and ester bond-containing group. And the like, and are preferably used.

Among the above norbornene monomers,
Dicyclopentadiene, dicyclopentadiene derivative,
Norbornene, ethylidene norbornene and norbornadiene are more preferably used, and among them, dicyclopentadiene is particularly preferably used. These norbornene monomers may be used alone or in combination of two or more.

The monocyclic cycloolefin is not particularly restricted but includes, for example, cyclobutene,
Cyclopentene, cyclooctene, cyclododecene, cyclopentadiene, cyclooctadiene, and the like,
Although it is preferably used, cyclooctadiene is more preferably used. These monocyclic cycloolefins may be used alone or in combination of two or more.

The metathesis polymerization catalyst used in the present invention does not deactivate even in the presence of oxygen, moisture, functional groups, etc.
The above-mentioned olefin metathesis-reactive monomer can be subjected to metathesis polymerization under a normal atmosphere in which oxygen or moisture is present, and is not particularly limited. For example, it is disclosed in US Pat. No. 5,831,108. Such a ruthenium-based complex, an osmium-based complex, a tungsten-based complex, and the like are mentioned, and are preferably used. Among them, a ruthenium-based complex is more preferably used because of its high activity and excellent heat resistance, oxygen resistance and reaction controllability. These metathesis polymerization catalysts may be used alone or in combination of two or more.

Specific examples of the ruthenium complex include, but are not particularly limited to, for example, ruthenium allyl complex, alkylidene complex, alkyne complex, alkene complex, isocyanide complex, oxo complex, carbine complex, carbene complex, carbonyl complex Examples include a complex, a chloro complex, a cyano complex, a thiocarbonyl complex, a nitrosyl complex, a dinitrogen complex, and a vinylidene complex, which are suitably used.
Among them, a ruthenium-carbene complex represented by the following general formula (1) and a ruthenium-carbene complex represented by the following general formula (2)
Vinylidene complexes and ruthenium-based complexes represented by the following general formulas (3) and (4) are particularly preferably used. These ruthenium-based complexes may be used alone or in combination of two or more.

[0033]

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In the general formula (1), R¹And R^TwoIs the same
One or different hydrogen atom, alkenyl having 2 to 20 carbon atoms
Group, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 6 to 20 carbon atoms.
Reel group, carboxyl group having 2 to 20 carbon atoms, 2 carbon atoms
To 20 alkoxy groups, alkenyl groups having 2 to 20 carbon atoms
Xy group, aryloxy group having 6 to 20 carbon atoms, 2 carbon atoms
An alkoxycarbonyl group having from 20 to 20 carbon atoms
Represents a thiolthio group or a ferrocene derivative, which are required.
If necessary, a halogen atom, an alkyl group having 1 to 5 carbon atoms
Or a phenyl group substituted by an alkoxy group having 1 to 5 carbon atoms.
It may be substituted by a phenyl group. Also, X¹as well as
X^TwoRepresents the same or different anionic ligands;¹Passing
And L^TwoRepresents the same or different neutral electron donors, and X¹,
X^Two, L ¹And L^TwoTwo or three of them are polydentate together
A rated ligand may be formed.

[0035]

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In the general formula (2), R ³ and R ⁴ are the same or different and each represent a hydrogen atom, an alkenyl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, Carboxyl group having 2 to 20 carbon atoms, 2 carbon atoms
Alkoxy group having 20 to 20 carbon atoms, alkenyloxy group having 2 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, 2 carbon atoms
To 20 alkoxycarbonyl groups, alkylthio groups having 2 to 20 carbon atoms, alkylsilyl groups having 2 to 20 carbon atoms, arylsilyl groups having 2 to 20 carbon atoms or ferrocene derivatives. Or a phenyl group substituted by an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. X ³ and X ⁴ represent the same or different anionic ligands; L ³ and L ⁴ represent the same or different neutral electron donors; and X ³ , X ⁴ , L ³ and L ⁴ Two or three may together form a multidentate chelating ligand.

[0037]

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[0038]

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In the general formulas (3) and (4),
R^Five, R⁶, R⁷And R⁸Are the same or different
Alkenyl group having 2 to 20 carbon atoms, 1 to 20 carbon atoms
Alkyl group, aryl group having 6 to 20 carbon atoms, 2 to 2 carbon atoms
20 carboxyl groups, alkoxy having 2 to 20 carbon atoms
Group, alkenyloxy group having 2 to 20 carbon atoms, 6 to 6 carbon atoms
20 aryloxy groups, alkoxy having 2 to 20 carbon atoms
A carbonyl group, an alkylthio group having 2 to 20 carbon atoms or
Herocene derivatives, which are optionally halogenated
Atom, an alkyl group having 1 to 5 carbon atoms or 1 to 5 carbon atoms
Substituted by a phenyl group substituted by an alkoxy group
It may be replaced. Also, Y¹, Y^TwoAnd Y ^ThreeIs the same or
Represents different sulfur, oxygen and selenium elements, and X^Five, X⁶,
X⁷And X⁸Represents the same or different anionic ligands
Then L^Five, L⁶, L⁷And L⁸Are the same or different neutral
Show children giving, X^Five, X⁶, X⁷, X⁸, L^Five,
L⁶, L⁷And L⁸Two or three of them are polydentate together
A rated ligand may be formed.

The ruthenium-based complexes represented by the general formulas (1) to (4) can be produced by various methods. For example, a coordination having L ^{1 to} L ⁸ or the like can be produced. The raw material precursor is synthesized by a known method, while the raw material of a ruthenium-based complex precursor is synthesized by a known method,
Finally, a desired ruthenium-based complex can be produced by mixing the two raw materials and performing a ligand exchange reaction.

The metathesis-polymerizable ruthenium-based complex represented by the general formulas (1) to (4) is a ruthenium-based metathesis polymerization catalyst which is stable in a normal atmosphere in the presence of oxygen and moisture. Other ruthenium-based metathesis polymerization catalysts may be used as long as they have the above properties.

The metathesis polymerization of an olefin metathesis reactive monomer represented by a norbornene-based monomer with a ruthenium-based metathesis polymerization catalyst has excellent stability against moisture of the ruthenium-based metathesis polymerization catalyst.
The polymerization itself is not hindered by moisture and shows good curability. On the other hand, radical polymerization using a peroxide-based polymerization catalyst such as an unsaturated polyester is susceptible to moisture and may cause poor curing.

The ruthenium-based complexes represented by the general formulas (1) to (4) are excellent in metathesis polymerization activity among the ruthenium-based metathesis polymerization catalysts. A metathesis polymer can be obtained.

These ruthenium-based complexes are preferably diluted with a solvent for use in improving the dispersibility of the olefin metathesis reactive monomer. Such a solvent is not particularly limited, and examples thereof include toluene, benzene, m-xylene, p-xylene, tetrahydrofuran, dichloromethane and the like, and are preferably used. These solvents may be used alone or in combination of two or more.

The amount of the metathesis polymerization catalyst typified by a ruthenium-based complex is not particularly limited.
For 1 mole of the olefin metathesis reactive monomer,
The amount of the metathesis polymerization catalyst is preferably from 1/5 to 1 / 1,000,000 mol, more preferably from 1/1000 to 1/100000 mol. Within the above range, the compounding amount of the metathesis polymerization catalyst may be set based on the necessary pot life (pot life) and curing time.

The layered silicate used in the present invention means a silicate mineral having an exchangeable metal cation in a crystal structure (interlayer).

The layered silicate is not particularly restricted but includes, for example, montmorillonite, saponite, hectorite, beidellite, stevensite,
Smectite-based clay minerals such as nontronite, vermiculite, halloysite, swellable mica, and the like are used, and are preferably used. Above all, montmorillonite and / or swellable mica are more preferably used. The layered silicate may be a natural product or a synthetic product. These layered silicates may be used alone or in combination of two or more.

As the above layered silicate, it is preferable to use smectites and swellable mica which have a large shape anisotropy effect defined by the following relational expression. By using a layered silicate having a large shape anisotropy effect such as smectites and swellable mica, the mechanical properties of the obtained layered silicate-reinforced olefin metathesis polymer become more excellent. Shape anisotropy effect = Area of crystal surface (A) / Area of crystal surface (B) In the above relational expression, the crystal surface (A) means a layer surface;
The crystal surface (B) means the side of the layer.

The shape of the layered silicate is not particularly limited, but preferably has an average length of 0.01 to 3 μm, a thickness of 0.001 to 1 μm and an aspect ratio of 20 to 500, More preferably, the average length is 0.0
It has a thickness of 5 to 2 μm, a thickness of 0.01 to 0.5 μm, and an aspect ratio of 50 to 200.

The exchangeable metal cations existing between the layers of the layered silicate are ions of metals such as sodium and calcium present on the crystal surface of the layered silicate, and these ions are cationic substances. Since it has an ion exchange property with the above, various substances having a cationic property can be inserted (intercalated) between the crystal layers of the layered silicate.

The cation exchange capacity of the layered silicate is not particularly limited, but may be 50 to 200 milliequivalent /
Preferably, it is 100 g. When the cation exchange capacity of the layered silicate is less than 50 milliequivalents / 100 g, the amount of the cationic substance inserted (intercalated) between the crystal layers of the layered silicate by ion exchange is reduced. May not be sufficiently depolarized, and conversely, the cation exchange capacity of the layered silicate may be 200 milliequivalents / 1.
If it exceeds 00 g, the bonding strength between the crystal layers of the layered silicate may be too strong, and the crystal flakes may not be easily separated.

In the present invention, it is preferable that the exchangeable metal cations existing between the layers of the layered silicate are ion-exchanged with a cationic surfactant in advance to be organically converted to be hydrophobic. By preliminarily making the interlayer of the layered silicate hydrophobic, the affinity between the layered silicate and the olefin metathesis polymer is increased, and the layered silicate can be finely dispersed more uniformly in the olefin metathesis polymer.

The cationic surfactant is not particularly restricted but includes, for example, quaternary ammonium salts and quaternary phosphonium salts, which are preferably used. Among them, since it is possible to sufficiently depolarize the crystal layer of the layered silicate, it is preferable to use a 4 layer having an alkyl chain having 6 or more carbon atoms.
A secondary ammonium salt (an alkyl ammonium salt having 6 or more carbon atoms) is more preferably used.

The quaternary ammonium salt is not particularly restricted but includes, for example, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl ammonium salt, distearyl dimethyl ammonium salt, di-hardened tallow dimethyl ammonium salt, Distearyldibenzylammonium salt, N-polyoxyethylene-N-lauryl-N, N-dimethylammonium salt and the like are mentioned, and are preferably used. These quaternary ammonium salts may be used alone or
More than one type may be used in combination.

The layered silicate used in the present invention can be improved in dispersibility in an olefin metathesis polymer by a chemical treatment as described above.

The above chemical treatment is not limited to the cation exchange method using a cationic surfactant (hereinafter, referred to as “chemical modification (1) method”). For example, various chemical treatment methods described below may be used. Can be implemented. The layered silicate having improved dispersibility in the olefin metathesis polymer by the following various chemical treatment methods including the chemical modification (1) method is hereinafter referred to as “organized layered silicate”.

(2) Chemical modification The hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the method (1) is converted into a functional group capable of chemically bonding to the hydroxyl group or a chemical group without chemical bonding. A method of chemically treating a compound having at least one functional group with high affinity at the molecular terminal (hereinafter referred to as “chemical modification (2)
Law ").

(3) Chemical modification The hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the method (1) is converted into a functional group capable of chemically bonding to the hydroxyl group or a chemical group without chemical bonding. A method of performing chemical treatment with a compound having one or more functional groups having high affinity and reactive functional groups at molecular terminals (hereinafter, referred to as
"Chemical modification (3) method").

(4) Chemical Modification A method of chemically treating the crystal surface of an organically modified layered silicate chemically treated by the method (1) with a compound having an anionic surface activity (hereinafter referred to as “chemical modification (4) method”). Described).

(5) Chemical modification In the method (4), a method of chemically treating a compound having one or more reactive functional groups in addition to an anion site in a molecular chain of a compound having anionic surface activity (hereinafter referred to as “chemical Modification (5) Method ").

(6) The organically modified layered silicate chemically treated by any one of the above-mentioned chemical modification methods (1) to (5) is further treated with, for example, a maleic anhydride-modified oligomer or the like. A method using a composition to which a polymer having a functional group capable of reacting with a layered silicate is added (hereinafter, referred to as a “chemical modification (6) method”) is exemplified. These chemical modification methods may be used alone or in combination of two or more.

In the above-mentioned chemical modification (2), the functional group capable of chemically bonding to a hydroxyl group or the functional group having high chemical affinity without chemical bonding is not particularly limited. Functional groups such as an alkoxy group, an epoxy group, a carboxyl group (including a dibasic acid anhydride), a hydroxyl group, an isocyanate group, and an aldehyde group, and other functional groups having high chemical affinity with a hydroxyl group. Can be

The functional group capable of chemically bonding to a hydroxyl group or a compound having a functional group having a high chemical affinity without chemical bonding is not particularly limited, and examples thereof include the functional groups exemplified above. Examples include a silane compound having a group, a titanate compound, a glycidyl compound, carboxylic acids, and alcohols, which are suitably used. These compounds may be used alone or in combination of two or more.

The silane compound is not particularly restricted but includes, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-aminopropyltrimethoxysilane, γ-amino Propylmethyldimethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-
Aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyldimethylethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, N-β- (Aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropyltriethoxysilane, N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane, octadecyltrimethoxysilane, octadecyl Triethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypro Le triethoxysilane and the like, is preferably used. These silane compounds may be used alone or in combination of two or more.

Further, the chemical modification (4) method and the chemical modification (5)
In the method, a compound having anionic surface activity and / or a compound having anionic surface activity and having at least one reactive functional group other than an anion site in a molecular chain includes a layered silicate by ionic interaction. Any compound may be used as long as it can chemically treat the salt, and is not particularly limited. For example, sodium laurate, sodium stearate, sodium oleate,
Higher alcohol sulfates, secondary higher alcohol sulfates, unsaturated alcohol sulfates, and the like are mentioned, and are preferably used. These compounds may be used alone or in combination of two or more.

The layered silicate used in the present invention has a wide angle X
It is preferably a layered silicate in which the average interlayer distance of the (001) plane measured by a line diffraction measurement method is 3 nm or more, and a part or all of the silicate is dispersed in five or less layers,
More preferably, it is a layered silicate in which the average interlayer distance is 6 nm or more and part or all of the layered silicate is dispersed in 5 layers or less. Incidentally, the average interlayer distance of the layered silicate referred to in the present invention means the average interlayer distance when a layer of fine flaky crystals of the layered silicate, X-ray diffraction peak and transmission electron microscopy, that is, Can be calculated by a wide-angle X-ray diffraction measurement method.

When the average interlayer distance of the layered silicate is 3 nm or more and part or all of the layered silicate is dispersed in 5 layers or less, the present invention can be obtained by dispersing the layered silicate in an olefin metathesis polymer. The layered silicate-reinforced olefin metathesis polymer of the present invention exhibits various properties such as excellent flame retardancy, mechanical properties and heat resistance.

The fact that the average interlayer distance of the layered silicate is 3 nm or more means that the interlayer of the layered silicate is cleaved to 3 nm or more. The fact that it is dispersed in 5 layers or less means
This means that a part or all of the layered silicate laminate is widely dispersed, which means that the interaction between the layers of the layered silicate is weakened.
The above effects can be obtained.

In particular, the average interlayer distance of the layered silicate is 6 nm.
With the above, the layered silicate-reinforced olefin metathesis polymer of the present invention obtained by dispersing the layered silicate in the olefin metathesis polymer has remarkably excellent properties such as flame retardancy, mechanical properties, and heat resistance. Is expressed. or,
The average interlayer distance of the layered silicate is 3 nm or more, preferably 6 nm.
If it is not less than nm, the crystal flake layer of the layered silicate separates layer by layer, and the interaction of the layered silicate becomes almost negligible, so that in the olefin metathesis polymer of the crystal flakes constituting the layered silicate Is advantageous in that the dispersion state of the particles proceeds in the direction of stabilization of crushing.

The fact that part or all of the layered silicate is dispersed in five layers or less means that more than 10% of the layered silicate is dispersed in five layers or less. And more preferably 20% or more of the layered silicate is dispersed in 5 layers or less.

The number of layers of the layered silicate is preferably 5 or less, whereby the above effect can be obtained. More preferably, the layered silicate is 3 or less. It is particularly preferable that the flakes are formed into a single layer.

In the layered silicate-reinforced olefin metathesis polymer of the present invention, the average interlayer distance of the layered silicate is 3 n
m or more, and if some or all of the layered silicate is dispersed in 5 layers or less, that is, if the layered silicate is highly dispersed in the olefin metathesis polymer, olefin metathesis is performed. The interface area between the polymer and the layered silicate increases, and the average distance between crystal flakes of the layered silicate decreases.

When the interface area between the olefin metathesis polymer and the phyllosilicate increases, the degree of constraint of the olefin metathesis polymer on the surface of the phyllosilicate increases,
Mechanical properties such as elasticity are improved. Further, when the degree of constraint of the olefin metathesis polymer on the surface of the layered silicate increases, the melt viscosity increases, and the moldability also improves. Further, gas barrier properties can be exhibited by the baffle plate effect of the layered silicate.

On the other hand, when the average distance between the crystal flakes of the layered silicate is reduced, a sintered body is easily formed by the movement of the crystal flakes of the layered silicate during combustion. That is, a layered silicate-reinforced olefin metathesis polymer in which crystal flakes of the layered silicate are dispersed such that the average interlayer distance is 3 nm or more facilitates formation of a sintered body that can be a flame-retardant film.
Since this sintered body is formed at an early stage of combustion, it can not only shut off the supply of oxygen from the outside world but also cut off the combustible gas generated by combustion. Polymers exhibit excellent flame retardancy.

The layered silicate-reinforced olefin metathesis polymer of the present invention is not particularly limited, but 100 parts by weight of the olefin metathesis polymer and 0.1% of the layered silicate.
It is preferable to contain 1 to 100 parts by weight, more preferably 1 to 20 parts by weight of the layered silicate.

If the content of the layered silicate is less than 0.1 part by weight with respect to 100 parts by weight of the olefin metathesis polymer, the mechanical properties and effects of various functions may not be sufficiently obtained. If the content of the layered silicate with respect to 100 parts by weight of the metathesis polymer exceeds 100 parts by weight, the density (specific gravity) of the layered silicate-reinforced olefin metathesis polymer becomes too high, and the practicability may be poor.

The layered silicate-reinforced olefin metathesis polymer of the present invention may contain, if necessary, a flame retardant other than the olefin metathesis polymer and the layered silicate, which are essential components, as long as the object of the present invention is not hindered. It is preferable that a flame retardant is blended in order to further improve the viscosity.

The flame retardant is not particularly restricted but includes, for example, phosphorus compounds, metal hydroxides, metal oxides, melamine derivatives and the like. And melamine derivatives are preferably used. These flame retardants may be used alone or in combination of two or more.

The phosphorus compound that can be used as a flame retardant is not particularly limited, and examples thereof include red phosphorus, ammonium polyphosphate, and a phosphorus compound represented by the following general formula (5). It is preferably used. These phosphorus compounds may be used alone or in combination of two or more. R ³ (R ² ) (OR ¹ ) P ＝ O Formula (5) (wherein R ¹ and R ³ represent a hydrogen atom, an alkyl group or an aryl group having 1 to 16 carbon atoms, and R ² represents hydrogen atom,
Hydroxyl group, alkyl group having 1 to 16 carbon atoms, alkoxy group,
Represents an aryl group or an aryloxy group, and R ¹ , R ^2, and R ³ may be the same or different from each other.) When the number of carbon atoms exceeds 16, the relative proportion of phosphorus is low. In some cases, the flame retardant effect may be insufficient.

The red phosphorus preferably has a surface coated with a resin from the viewpoint of improving moisture resistance and preventing spontaneous ignition when kneading after being added to the olefin metathesis reactive monomer. Further, the ammonium polyphosphate may have been subjected to a surface treatment such as melamine modification.

The phosphorus compound represented by the general formula (5) is not particularly limited. Examples thereof include methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, and butyl. Phosphonic acid, 2-methylpropylphosphonic acid, t-butylphosphonic acid, 2,3-dimethylbutylphosphonic acid, octylphosphonic acid, phenylphosphonic acid,
Dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenylphosphinic acid, diethylphenylphosphinic acid, diphenylphosphinic acid, bis (4-methoxyphenyl) phosphinic acid, etc. No.

The amount of the phosphorus compound is not particularly limited, but is preferably 0.5 to 0.5 parts by weight based on 100 parts by weight of the olefin metathesis reactive monomer.
It is preferably 100 parts by weight, more preferably 2 parts by weight.
５０50 parts by weight.

Olefin metathesis reactive monomer 10
If the amount of the phosphorus compound is less than 0.5 part by weight relative to 0 part by weight, sufficient flame retardancy may not be obtained,
Conversely, if the amount of the phosphorus compound exceeds 100 parts by weight with respect to 100 parts by weight of the olefin metathesis reactive monomer, the mechanical properties of the layered silicate reinforced olefin metathesis polymer may decrease.

The metal hydroxide that can be used as a flame retardant is not particularly limited, but, for example, magnesium hydroxide, aluminum hydroxide, dawsonite,
Calcium aluminate, dihydrate gypsum, calcium hydroxide and the like are mentioned, and are preferably used. Among them, magnesium hydroxide and aluminum hydroxide are more preferably used. These metal hydroxides may be used alone or in combination of two or more. When two or more metal hydroxides are used in combination, the decomposition dehydration reaction is started at different temperatures, so that a higher flame retardant effect can be obtained. These metal hydroxides have been subjected to surface treatment with a surface treatment agent such as a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, a polyvinyl alcohol-based surface treatment agent, or an epoxy-based surface treatment agent. Is also good.

The metal hydroxide causes an endothermic dehydration reaction under high heat during combustion, absorbs heat and releases water molecules, thereby lowering the temperature of the combustion field and exhibiting the effect of extinguishing fire. In the present invention, since the layered silicate is mixed with the olefin metathesis polymer, the flame retardant effect of the metal hydroxide is increased. This is because the flame-retarding effect of the layered silicate due to the formation of a film during combustion and the flame-retarding effect of the metal hydroxide due to the endothermic dehydration reaction occur competitively and promote each effect.

The blending amount of the metal hydroxide is not particularly limited, but the metal hydroxide is added in an amount of 0.5 to 0.5 parts by weight based on 100 parts by weight of the olefin metathesis reactive monomer.
It is preferably 100 parts by weight, more preferably 2 parts by weight.
0 to 60 parts by weight.

Olefin metathesis reactive monomer 10
If the amount of the metal hydroxide is less than 0.5 part by weight based on 0 part by weight, sufficient flame retardancy may not be obtained,
Conversely, if the amount of the metal hydroxide exceeds 100 parts by weight based on 100 parts by weight of the olefin metathesis reactive monomer, the density (specific gravity) of the layered silicate-reinforced olefin metathesis polymer increases, or the flexibility is impaired. Demerits such as may occur.

The melamine derivative which can be used as a flame retardant is not particularly limited, and examples thereof include melamine, melamine cyanurate, melamine isocyanurate, melamine phosphate and the like, and those obtained by subjecting these to a surface treatment. And the like, and are preferably used. These melamine derivatives may be used alone or in combination of two or more.

The amount of the melamine derivative to be compounded is not particularly limited, but the melamine derivative is added in an amount of 100 parts by weight of the olefin metathesis-reactive monomer.
It is preferably from 5 to 100 parts by weight, more preferably from 1 to 30 parts by weight.

Olefin metathesis reactive monomer 10
If the amount of the melamine derivative is less than 0.5 part by weight with respect to 0 part by weight, sufficient flame retardancy may not be obtained, and conversely, the amount of the melamine derivative with respect to 100 parts by weight of the olefin metathesis reactive monomer may be insufficient. If it exceeds 100 parts by weight, the mechanical properties of the layered silicate-reinforced olefin metathesis polymer may be reduced, or the formation of a combustion film of the layered silicate during combustion may be hindered.

The layered silicate-reinforced olefin metathesis polymer of the present invention has the object of achieving the object of the present invention, in addition to the essential components of the olefin metathesis polymer and the layered silicate, and the above-mentioned flame retardant compounded as required. If necessary, a viscosity modifier may be blended as long as the viscosity is not hindered.

The viscosity modifier is preferably a reactive viscosity modifier which can be incorporated into the olefin metathesis polymer during the metathesis polymerization of the olefin metathesis reactive monomer, and is not particularly limited.
Examples thereof include polybutadiene and polyisoprene having an olefinically unsaturated group, which are suitably used. These viscosity modifiers may be used alone or in combination of two or more. The amount of the viscosity modifier is not particularly limited, but is preferably 0.1 to 50% by weight, more preferably 0.1 to 20% by weight based on the total amount of the olefin metathesis reactive monomer. is there.

Further, the layered silicate-reinforced olefin metathesis polymer of the present invention contains, in addition to the essential components, an olefin metathesis polymer and a layered silicate, and a flame retardant and a viscosity modifier which are optionally added. If necessary within the range not hindering the achievement of the problem, for example, fillers such as calcium carbonate, talc, clay, magnesium carbonate, sodium hydrogen carbonate, fly ash, silica sand for increasing the amount or adjusting the viscosity, a molecular weight modifier, Polymer modifier, thixotropic agent, softener, plasticizer, lubricant, antistatic agent, antifogging agent,
One or more of various additives such as a coloring agent, an antioxidant (antiaging agent), a heat stabilizer, a light stabilizer, an ultraviolet absorber, and an antifoaming agent may be blended.

The phyllosilicate-reinforced olefin metathesis polymer of the present invention was subjected to a combustion test according to ASTM E 1354 under a radiation heating condition of 50 kW / m ^2.
The combustion residue burned by heating for 0.5 min.
The yield point stress when compressed at 1 cm / s is preferably 4.9 kPa or more, more preferably 15.0 kP.
a or more.

When the yield point stress of the combustion residue of the layered silicate-reinforced olefin metathesis polymer is less than 4.9 kPa, the combustion residue is liable to collapse with a small force, and the layered silicate-reinforced olefin metathesis polymer has a low yield point. Flame retardancy may be insufficient. That is, in order for the sintered body of the layered silicate-reinforced olefin metathesis polymer of the present invention to sufficiently exhibit the function as a flame retardant film, the sintered body must have a yield point stress of 4.9 kPa or more and be fired until the end of combustion. It is preferred that the body retains its shape.

Next, a method for producing the layered silicate-reinforced olefin metathesis polymer of the present invention will be described.

The method for producing a layered silicate-reinforced olefin metathesis polymer of the present invention comprises dispersing and mixing a layered silicate in an olefin metathesis-reactive monomer and polymerizing the resulting mixture in the presence of a metathesis polymerization catalyst. (Hereinafter referred to as “first manufacturing method”).

The process for producing a layered silicate-reinforced olefin metathesis polymer according to the present invention comprises inserting a metathesis polymerization catalyst into a layered silicate (intercalating), and converting the obtained layered silicate into a olefin metathesis polymer. It is characterized by being dispersed and mixed in a reactive monomer and polymerized (hereinafter referred to as "second production method").

(1) First Production Method In the first production method, a layered silicate is first dispersed and mixed in an olefin metathesis reactive monomer. The method is not particularly limited, for example,
A method in which the layered silicate and the monomer are previously mixed is exemplified. In this way, by previously mixing the layered silicate and the monomer, the layered silicate is sufficiently swollen in the monomer,
Can be dispersed. Therefore, a layered silicate-reinforced olefin metathesis polymer in which the layered silicate is finely dispersed in the olefin metathesis polymer can be efficiently and easily obtained at the time of the next step of polymerization. In the case of this method, the whole amount of the monomer and the layered silicate may be mixed at once, or a part of the monomer and the whole amount of the layered silicate may be mixed, and then the remaining amount of the monomer may be added and mixed. May be.

The apparatus for mixing the monomer and the layered silicate is not particularly limited. Examples thereof include a planetary stirring apparatus, a wet mechanochemical apparatus, a Henschel mixer, a homogenizer, an ultrasonic irradiator, and a static mixer. Is mentioned.

Next, a metathesis polymerization catalyst is added to a dispersion mixture of the monomer and the layered silicate to polymerize the monomer, whereby a desired layered silicate-reinforced olefin metathesis polymer can be produced. In this case, it is preferable to control the polymerization rate by heating the polymerization vessel or polymerization type (molding type) or the above-mentioned dispersion mixed solution to 30 to 150 ° C. as necessary.

(2) Second Production Method In the second production method, first, a metathesis polymerization catalyst is inserted (intercalated) into a layered silicate. After obtaining the layered silicate supporting the metathesis polymerization catalyst in this way, by dispersing and mixing the layered silicate in the olefin metathesis-reactive monomer, the monomer can sufficiently penetrate between the layers of the layered silicate. For this reason, at the time of the polymerization which is the next step, the polymerization starts from between the layers of the layered silicate, and the layered silicate-reinforced olefin metathesis polymer in which the layered silicate is finely dispersed in the olefin metathesis polymer is efficiently and efficiently formed. Can be easily obtained.

The method for inserting (intercalating) the metathesis polymerization catalyst into the layered silicate is not particularly limited. For example, a method in which the layered silicate and the metathesis polymerization catalyst are rubbed with a Meneau mortar, And a method in which a metathesis polymerization catalyst is dispersed (dispersed) in a layered silicate in a solvent such as water or an organic solvent.

Next, the layered silicate in which the metathesis polymerization catalyst is inserted (intercalated) is dispersed and mixed in the monomer, and the monomer is polymerized in the same manner as in the first production method, whereby the desired layered silicate is obtained. Salt-reinforced olefin metathesis polymers can be produced.

In the production method of the present invention (the first production method and the second production method), the polymerization of the olefin metathesis-reactive monomer may be carried out in a solvent compatible with the monomer. It may be performed in a solvent that is not compatible with the monomer.

The solvent compatible with the monomer is not particularly limited, but examples thereof include saturated hydrocarbon organic solvents such as pentane and hexane, aromatic organic solvents such as benzene and toluene, methylene chloride, and the like. Halogenated organic solvents such as chloroform, diethyl ether, ether organic solvents such as 1,2-dimethoxyethane, methyl acetate,
Ester organic solvents such as ethyl acetate are exemplified.
Further, the solvent having no compatibility with the monomer is not particularly limited, and examples thereof include water and alcohol. These solvents may be used alone,
Two or more types may be used in combination.

The polymerization of the monomer is not particularly limited, but is preferably performed in an atmosphere of an inert gas such as nitrogen gas. However, when the ruthenium-based complex is used as a metathesis polymerization catalyst, Can be polymerized in air.

In general, an oligomer obtained by a metathesis polymerization reaction has an unsaturated double bond, and may be deteriorated by oxygen in the air. May be added with an antioxidant.

The antioxidant that can be added to the metathesis polymerization reaction system may be any antioxidant as long as it does not participate in the polymerization reaction, and is not particularly limited. For example, pentaerythritol tetrakis [3- (3-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,
4,6-tris (3,5-tert-butyl-4-hydroxybenzyl) benzene, 2,6-di-tert-butyl-4-methylphenol, tris (3,5-di-tert-butyl-4)
-Hydroxybenzyl) isocyanurate, 1,3,5
-Tris (4-tert-butyl-3-hydroxy-2,6-
Dimethyldibenzyl) isocyanurate and the like,
It is preferably used. These antioxidants may be used alone or in combination of two or more.

When the metathesis polymerization reaction is carried out using a ruthenium-based complex represented by any one of the above-mentioned general formulas (1) to (4) as a metathesis polymerization catalyst, these ruthenium-based complexes are converted to a metathesis polymerization reaction. Since it is suitably used not only as a catalyst but also as a hydrogenation catalyst, the oligomer synthesis step and the hydrogenation step can be performed continuously. The hydrogenation is carried out in a homogeneous or heterogeneous system, usually under a hydrogen pressure of 1 to 200 atm and a temperature of 0 to 250 ° C, depending on the type of the metathesis polymerization catalyst.

The physical properties (mechanical properties, heat resistance, gas barrier properties and transparency) of the layered silicate-reinforced olefin metathesis polymer obtained by the production method of the present invention are generally as follows:
It can be said that the finer the layered silicate is dispersed in the olefin metathesis polymer, the more the above-mentioned physical properties of the layered silicate reinforced olefin metathesis polymer (olefin metathesis polymer-layered silicate composite material) are improved. This can be explained by the relationship between the increase in the aspect ratio of the layered silicate and the increase in the interface area between the layered silicate and the olefin metathesis polymer, and the improvement in the dispersibility of the layered silicate. That is, by restricting the molecular motion of the olefin metathesis polymer at the interface between the olefin metathesis polymer and the layered silicate, the mechanical properties such as the elastic modulus of the olefin metathesis polymer and the heat resistance are improved. The higher the degree of dispersion of the salt, the more efficiently the physical properties of the olefin metathesis polymer can be improved. In addition, since gas molecules are more permeable to the olefin metathesis polymer layer than inorganic materials, when the gas molecules diffuse in the layered silicate reinforced olefin metathesis polymer, they diffuse while bypassing the inorganic material. Therefore, the higher the degree of dispersion of the layered silicate, the more efficiently the gas barrier property can be improved. Furthermore, when a layered silicate is blended with a highly transparent olefin metathesis polymer, if the size of the dispersed layered silicate is large, light is scattered and becomes opaque, but the layered silicate becomes fine. The more the particles are dispersed, the smaller the scattering of light and the higher the transparency. Further, the thermal dimensional stability, like the mechanical properties, is significantly improved as the degree of dispersion of the layered silicate is improved.

[0112]

Since the layered silicate-reinforced olefin metathesis polymer of the present invention contains the olefin metathesis polymer and the layered silicate, a sintered body is formed by the layered silicate during combustion, and the shape of the combustion residue is reduced. Will be retained. Thereby, shape collapse does not occur even after combustion, and it is possible to prevent fire spread.

Therefore, the layered silicate-reinforced olefin metathesis polymer of the present invention and the molded article made of the polymer exhibit excellent flame retardancy. Further, since the layered silicate can impart excellent flame retardancy to the olefin metathesis polymer without adding it in a large amount as in a normal flame retardant, the above-mentioned polymer and molded article have excellent mechanical properties and Can maintain transparency. Further, the layered silicate-reinforced olefin metathesis polymer of the present invention has improved physical properties such as elastic modulus and gas barrier properties, and has improved heat resistance based on an increase in heat deformation temperature due to restraint of molecular chains. Improvements in dimensional stability and the like based on a nucleating agent effect by salt crystals are also being made.

According to the production method of the present invention, the polymerization is carried out in a state where the monomer has entered between the layers of the layered silicate.
It is possible to finely disperse the layered silicate, and thus it is possible to efficiently and easily obtain a layered silicate-reinforced olefin metathesis polymer having the above-mentioned excellent properties by blending a relatively small amount of the layered silicate. it can.

[0115]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” means “parts by weight”.

In this example, the following raw materials were used. 1. 1. Olefin metathesis reactive monomer (1) dicyclopentadiene (2) ethylidene norbornene Metathesis polymerization catalyst (1) Ruthenium complex (a): US Pat. No. 5,831,311
A ruthenium-based complex represented by the following formula (6), which was synthesized in accordance with JP 08-A-08-A.

Embedded image (In the formula, Cy represents a cyclohexyl group.) (2) Ruthenium-based complex (b): 5.57 g (9.1 m)
mol) of Ru (p-cymene) Cl ₂ ,
18.2 mmol of PCy ₃ and 9.1 mmol of 1-
Trimethylsilylhexine was mixed with 150 ml of toluene (solvent) in a 300 ml flask under a stream of nitrogen.
A ruthenium-based complex represented by the following formula (7), which was synthesized by removing toluene under reduced pressure after reacting for an hour and performing recrystallization in a tetrahydrofuran / ethanol-based solvent.

Embedded image (In the formula, Cy represents a cyclohexyl group, Me represents a methyl group, and nBu represents an n-butyl group.) Layered silicate (1) Montmorillonite: trade name "Bengel A" (manufactured by Toyshun Mining Co., Ltd.). (2) Swellable mica: trade name "ME-100" (manufactured by Corp Chemical). (3) DSDM-modified montmorillonite: Organized montmorillonite (trade name "New Esven D", manufactured by Toyshun Mining Co., Ltd.) obtained by ion-exchange of all sodium ions between montmorillonite layers with distearyl dimethyl ammonium chloride (DSDM). (4) DSDM-modified swelling mica: Organized swelling mica (trade name "MAE-100", which is obtained by ion-exchanging the total amount of sodium ions between swelling mica layers by DSDM)
Corp Chemical Co.).

(Example 1) A mixed monomer liquid in which dicyclopentadiene and ethylidene norbornene were mixed at a molar ratio of 90:10 was used as the olefin metathesis reactive monomer. Montmorillonite “Bengel A” was used as the layered silicate, weighed so as to have a filling rate of 5% by weight with respect to the mixed monomer liquid, mixed and dispersed in the mixed monomer liquid. Then, a metathesis polymerization catalyst solution obtained by dissolving 10 parts by weight of a ruthenium-based complex (a) in 200 parts by weight of toluene (solvent) in the obtained mixed dispersion was mixed with the ruthenium complex (a) based on the mixed monomer liquid.
Were mixed so as to have a molar ratio of 1/10000, and stirred and mixed to prepare an olefin metathesis reactive monomer composition. Then, immediately, the obtained olefin metathesis-reactive monomer composition was poured into a mold so as to have a suitable thickness (2 mm, 3 mm, 25 μm) as a test piece for evaluation (2 mm and 3 mm in thickness) or applied (25 μm in thickness). ) And put in an oven at 60 ° C for 10
Polymerization was carried out for 1 minute to produce test pieces for evaluation.

(Example 2) An olefin metathesis reaction was performed in the same manner as in Example 1 except that DSDM-modified montmorillonite "New Sven D" was used instead of montmorillonite "Benger A" as the layered silicate. The reactive monomer composition and each test piece for evaluation were produced.

Example 3 Instead of montmorillonite "Bengel A", swellable mica "M" was used as the layered silicate.
An olefin metathesis-reactive monomer composition and test pieces for evaluation were prepared in the same manner as in Example 1 except that "E-100" was used.

(Example 4) Olefin metathesis was carried out in the same manner as in Example 1 except that DSDM-modified swellable mica "MAE-100" was used instead of montmorillonite "Bengel A" as the layered silicate. A reactive monomer composition and test pieces for evaluation were prepared.

(Example 5) Ruthenium-based complex (a) as a metathesis polymerization catalyst was weighed with respect to montmorillonite "Bengel A" as a layered silicate so as to be 2% by weight, and both were weighed in a mortar made of Meneau. Ruthenium-based complex (a) was inserted (intercalated) between layers of montmorillonite “Bengel A” by rubbing while mixing. An olefin metathesis-reactive monomer composition and test pieces for evaluation were prepared in the same manner as in Example 1 except that the montmorillonite “Bengel A” into which the ruthenium-based complex (a) was inserted was used.

Example 6 An olefin metathesis reaction was carried out in the same manner as in Example 5 except that DSDM-modified montmorillonite “New Sven D” was used as the layered silicate instead of montmorillonite “Benger A”. The reactive monomer composition and each test piece for evaluation were produced.

(Example 7) Instead of montmorillonite "Bengel A", swellable mica "M" was used as the layered silicate.
An olefin metathesis-reactive monomer composition and test pieces for evaluation were prepared in the same manner as in Example 5 except that "E-100" was used.

Example 8 Olefin metathesis was performed in the same manner as in Example 5 except that DSDM-modified swellable mica “MAE-100” was used instead of montmorillonite “Bengel A” as the layered silicate. A reactive monomer composition and test pieces for evaluation were prepared.

(Example 9) As a metathesis polymerization catalyst,
An olefin metathesis-reactive monomer composition and test pieces for evaluation were produced in the same manner as in Example 1 except that the ruthenium-based complex (b) was used instead of the ruthenium-based complex (a).

Example 10 As the olefin metathesis-reactive monomer, dicyclopentadiene and 1,5-diene were mixed in place of the mixed monomer liquid obtained by mixing dicyclopentadiene and ethylidene norbornene at a molar ratio of 90:10.
An olefin metathesis-reactive monomer composition and test pieces for evaluation were prepared in the same manner as in Example 1 except that a mixed monomer liquid obtained by mixing cyclooctadiene with a molar ratio of 95: 5 was used.

Example 11 The procedure of Example 1 was repeated except that 40 parts by weight of magnesium hydroxide (trade name “Kisma 5J”, manufactured by Kyowa Chemical Co., Ltd.) was added to 100 parts by weight of the olefin metathesis reactive monomer. In the same manner as in the above, an olefin metathesis reactive monomer composition and test pieces for each evaluation were prepared.

(Comparative Example 1) An olefin metathesis-reactive monomer composition and a test piece for evaluation were prepared in the same manner as in Example 1 except that montmorillonite “Bengel A” as a layered silicate was not blended. Produced.

Using the test pieces for evaluation obtained in Examples 1 to 11 and Comparative Example 1, the performance (average interlayer distance of layered silicate, film strength of combustion residue, bending strength) was determined by the following method. The elastic modulus, bending strength, coefficient of linear expansion, moisture permeability, heat deformation temperature) were evaluated. The results were as shown in Table 1.

Average interlayer distance of layered silicate: Obtained from the diffraction of the laminated surface of the layered silicate in a 3 mm-thick test piece using an X-ray diffractometer (trade name “RINT1100”, manufactured by Rigaku Corporation). The 2θ of the diffraction peak obtained was measured and the (001) of the layered silicate was determined by the following black diffraction equation.
The surface distance (d) is calculated, and the obtained d is used as the average interlayer distance (n).
m). λ = 2 dsin θ (where λ: 1.54, d: interplanar spacing of layered silicate, θ:
Diffraction angle)

Coating strength of combustion residue: ASTM E 1
According to 354 “Testing method for flammability of building materials”, 10
A test piece for evaluation having a thickness of 3 mm cut into 0 mm × 100 mm was irradiated with a 50 kW / m ² heat ray by a cone calorimeter and burned. After the completion of the combustion, the combustion residue was compressed at a speed of 0.1 cm / s using a strength measuring device, and the film strength (kPa) of the combustion residue was measured.

Flexural modulus and flexural strength: JIS
In accordance with K-7203 "Bending test method of hard plastic", a test piece for measurement is cut out from a test piece for evaluation having a thickness of 2 mm, and a bending elastic modulus (GPa) and a bending strength (MPa) are obtained using a Tensilon tester. Was measured.

Coefficient of linear expansion: A test piece for measurement was cut out from a test piece for evaluation having a thickness of 2 mm, and a TMA tester (SEIK) was used.
The average linear expansion coefficient (1 × 10 ⁻⁵ / ° C.) in a temperature range of 20 to 80 ° C. was measured using O Scientific Co., Ltd.).

Moisture Permeability: The moisture permeability (g / m ² · 24 hours) of a 25 μm-thick test piece was measured in accordance with JIS Z-0208 “Test Method for Moisture Permeability of Moisture-Proof Packaging Material (Cup Method)”. did.

Heat deformation temperature: Heat deformation temperature (° C.) of an evaluation test piece having a bending stress of 181.3 N / cm ² and a thickness of 3 mm in accordance with JIS K-7207 “Test method for deflection temperature under load of hard plastic”. Was measured.

[0136]

[Table 1]

As is clear from Table 1, in the test specimens composed of the layered silicate-reinforced olefin metathesis polymers of Examples 1 to 11 according to the present invention, the average interlayer distance of the layered silicate was 3 nm or more ( (3.5 nm or more), it was easy to form a sintered body that could be a flame-retardant film. In addition, all of the test pieces for evaluation composed of the layered silicate-reinforced olefin metathesis polymer had a film strength of the combustion residue of 4.9 kPa or more, which was high.

Each of the evaluation test pieces composed of the layered silicate-reinforced olefin metathesis polymer had high flexural modulus and flexural strength and exhibited excellent mechanical properties.
In addition, each of the test pieces for evaluation has a low linear expansion coefficient,
Excellent dimensional stability was developed. In addition, each of the test pieces for evaluation had a high heat deformation temperature and exhibited excellent heat resistance. Further, all of the test pieces for evaluation had low moisture permeability and exhibited excellent gas barrier properties.

On the other hand, in the test specimen for evaluation made of the olefin metathesis polymer of Comparative Example 1 in which the layered silicate was not blended, the combustion residue did not form a film. Further, the test specimen for evaluation made of the olefin metathesis polymer,
The flexural modulus and flexural strength were low, and the mechanical properties were poor. The test piece for evaluation had a high coefficient of linear expansion and poor dimensional stability. Further, the test piece for evaluation had a low heat distortion temperature and was inferior in heat resistance. Furthermore, the test piece for evaluation had high moisture permeability and inferior gas barrier properties.

[0140]

As described above, the layered silicate-reinforced olefin metathesis polymer of the present invention has various properties such as excellent mechanical properties, dimensional stability, heat resistance, flame retardancy and gas barrier properties. Therefore, for example, automobile parts such as bumpers and instrument panels; housing equipment such as bathtubs and waterproof pans; housing members such as water pipes (water distribution pipes), sewer pipes (drain pipes), and electric equipment; sports equipment and leisure equipment; It is suitably used as a molding material for manholes, septic tank members and the like.

Further, according to the production method of the present invention, a layered silicate-reinforced olefin metathesis polymer having the above-mentioned various excellent properties can be obtained efficiently and easily.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/53 C08K 5/53 (72) Inventor Nobuhiro Goto 2-2 Kamikoba Kamichocho Minami-ku, Kyoto-shi Sekisui Kagaku Kogyo Co., Ltd. (72) Inventor Masafumi Nakatani 2-2 Kami-Tokagamichokomachi, Minami-ku, Kyoto Sekisui Kagaku Kogyo Co., Ltd. F-term (reference) 4J002 CE001 DA057 DE077 DE087 DE147 DE187 DG057 DH057 DJ006 EU187 EW127 EW137 FD010 FD137

Claims (15)

[Claims] 1. A layered silicate-reinforced olefin metathesis polymer comprising an olefin metathesis polymer obtained by polymerizing an olefin metathesis-reactive monomer with a metathesis polymerization catalyst, and a layered silicate. 2. The layered silicate-reinforced olefin metathesis polymer according to claim 1, comprising 100 parts by weight of the olefin metathesis polymer and 0.1 to 100 parts by weight of the layered silicate. 3. The olefin metathesis-reactive monomer is a norbornene monomer and / or a monocyclic cycloolefin.
6. The layered silicate-reinforced olefin metathesis polymer according to item 1. 4. The method according to claim 3, wherein the norbornene-based monomer is at least one type of norbornene-based monomer selected from the group consisting of dicyclopentadiene, a dicyclopentadiene derivative, norbornene, ethylidene norbornene, and norbornadiene. The layered silicate-reinforced olefin metathesis polymer according to the above. 5. The layered silicate-reinforced olefin metathesis polymer according to claim 3, wherein the monocyclic cycloolefin is cyclooctadiene. 6. An olefin metathesis reactive monomer 1.
At least one selected from the group consisting of a phosphorus compound, a metal hydroxide and a melamine derivative with respect to 00 parts by weight.
The layered silicate-reinforced olefin metathesis polymer according to any one of claims 1 to 5, wherein 0.5 to 100 parts by weight of a kind of flame retardant is blended. 7. The layered silicate-reinforced olefin metathesis polymer according to claim 1, wherein the metathesis polymerization catalyst is a ruthenium-based complex. 8. A ruthenium-based complex represented by the following general formula (1)
~ At least one kind of ruthenium represented by the general formula (4)
The layered silica according to claim 7, which is a complex.
A salt-reinforced olefin metathesis polymer. Embedded imageＲ In the general formula (1), R¹And R^TwoAre the same or different, water
Elemental atom, alkenyl group having 2 to 20 carbon atoms, 1 to 2 carbon atoms
0 alkyl group, 6-20 carbon aryl group, carbon number
Alkoxy having 2 to 20 carboxyl groups and 2 to 20 carbon atoms
Si group, alkenyloxy group having 2 to 20 carbon atoms, 6 carbon atoms
~ 20 aryloxy groups, C2-20 alkoxy
A cyclocarbonyl group, an alkylthio group having 2 to 20 carbon atoms or
Ferrocene derivatives, which may optionally be
Gen atom, alkyl group having 1 to 5 carbon atoms or 1 to 5 carbon atoms
By a phenyl group substituted by an alkoxy group of
It may be replaced. Also, X¹And X^TwoAre the same or different
An anionic ligand represented by L¹And L^TwoAre the same or
Showing different neutral electron donors, X¹, X^Two, L¹And L
^TwoTwo or three of which together form a polydentate chelating ligand
It may be formed.中 In the general formula (2), R^ThreeAnd R^FourAre the same or different, water
Elemental atom, alkenyl group having 2 to 20 carbon atoms, 1 to 2 carbon atoms
0 alkyl group, 6-20 carbon aryl group, carbon number
Alkoxy having 2 to 20 carboxyl groups and 2 to 20 carbon atoms
Si group, alkenyloxy group having 2 to 20 carbon atoms, 6 carbon atoms
~ 20 aryloxy groups, C2-20 alkoxy
Cicarbonyl group, alkylthio group having 2 to 20 carbon atoms, charcoal
A C 2-20 alkylsilyl group, a C 2-20 alkyl
Represents a reelsilyl group or a ferrocene derivative,
If necessary, halogen atom, alkyl having 1 to 5 carbon atoms
Substituted by a group or an alkoxy group having 1 to 5 carbon atoms
It may be substituted by a phenyl group. Also, X^ThreePassing
And X^FourRepresents the same or different anionic ligands; ^Three
And L^FourRepresents the same or different neutral electron donors,
X^Three, X^Four, L^ThreeAnd L^FourTwo or three of
A polydentate chelating ligand may be formed.Embedded image中 In the general formulas (3) and (4), R^Five, R⁶, R⁷
And R⁸Are the same or different, a hydrogen atom, having 2 to 20 carbon atoms
Alkenyl group, alkyl group having 1 to 20 carbon atoms, carbon number
6-20 aryl groups, carboxyls having 2-20 carbon atoms
Group, an alkoxy group having 2 to 20 carbon atoms, an alkoxy group having 2 to 20 carbon atoms
Alkenyloxy group, aryloxy having 6 to 20 carbon atoms
Group, alkoxycarbonyl group having 2 to 20 carbon atoms, carbon number
Represents 2 to 20 alkylthio groups or ferrocene derivatives
However, these may be, if necessary, a halogen atom, a
An alkyl group having 5 or an alkoxy group having 1 to 5 carbon atoms.
May be substituted by a substituted phenyl group
No. Also, Y¹, Y^TwoAnd Y^ThreeAre the same or different sulfur and acid
Element, selenium element, X^Five, X⁶, X⁷And X⁸Is the same
Represents one or a different anionic ligand;^Five, L⁶, L
⁷And L⁸Represents the same or different neutral electron donors, and X
^Five, X⁶, X⁷, X⁸, L^Five, L⁶, L⁷And L⁸Within
Two or three of together form a multidentate chelating ligand
May be 9. The method according to claim 9, wherein the layered silicate is montmorillonite and / or montmorillonite.
9. The layered silicate-reinforced olefin metathesis polymer according to claim 1, wherein the polymer is swellable mica. 10. The phyllosilicate according to claim 1, wherein the phyllosilicate is an phyllosilicate obtained by ion-exchanging exchangeable metal cations contained in its crystal structure with a cationic surfactant. Item 10. The layered silicate-reinforced olefin metathesis polymer according to any one of Items 9 to 10. 11. The layered silicate-reinforced olefin metathesis according to claim 1, wherein the layered silicate is a layered silicate containing an alkylammonium ion having 6 or more carbon atoms. Polymer. 12. The layered silicate in which the layered silicate has an average interlayer distance of (001) plane measured by a wide-angle X-ray diffraction measurement method of 3 nm or more, and part or all of the layered silicate is dispersed in five or less layers. The layered silicate-reinforced olefin metathesis polymer according to any one of claims 1 to 11, which is a salt. 13. Under a radiant heating condition of 50 kW / m ² ,
The yield point stress when compressing the combustion residue burned by heating for 0 minute (according to ASTM E1354) at a speed of 0.1 cm / s is 4.9 kPa or more. 13. The layered silicate-reinforced olefin metathesis polymer according to any one of 12. 14. The method according to claim 1, wherein the layered silicate is dispersed and mixed in an olefin metathesis reactive monomer, and the resulting mixture is polymerized in the presence of a metathesis polymerization catalyst. 3. The method for producing a layered silicate-reinforced olefin metathesis polymer according to item 1. 15. A method comprising inserting (intercalating) a metathesis polymerization catalyst into a layered silicate and dispersing and mixing the obtained layered silicate with a metathesis polymerization catalyst in an olefin metathesis-reactive monomer to carry out polymerization. A method for producing a layered silicate-reinforced olefin metathesis polymer according to any one of claims 1 to 13.