JP2002338792A - Method for producing norbornene-based resin molded article and synthetic wood - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for safely producing a norbornene-based resin molded product having a woody feel and capable of performing processing such as cutting and cutting in the same manner as wood with good productivity. SOLUTION: 0.5 to 20% by metathesis catalyst
The present invention provides a method for producing a norbornene-based resin molded article by bulk-polymerizing a norbornene-based monomer in the presence of wood powder containing water. Synthetic wood is also provided by the method of the present invention.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a norbornene-based resin molded product, and more particularly, to a method for producing a norbornene-based resin molded product in which a norbornene-based monomer is bulk-polymerized in the presence of wood flour using a metathesis catalyst. . The present invention also relates to a synthetic wood obtained by such a production method.

[0002]

2. Description of the Related Art A reaction molding method (RIM = reaction injection molding method, RTM = resin transfer molding method, etc.) for performing bulk polymerization in a mold using a reaction stock solution containing a norbornene-based monomer and a metathesis catalyst is known. , A well-known technology (Japanese Patent
-37568). According to this method, a large-sized molded body can be obtained with a simple mold and molding apparatus as compared with a thermoplastic resin injection molding method.

[0003] On the other hand, for architectural and construction purposes,
A molded article having a tactile feel and appearance (also referred to as a woody feel) like wood is required, and is used as a synthetic wood for wood replacement. In order to impart a woody feel to various resin molded articles, it is common to use a mixed material with wood flour. Further, if a mixed material with wood flour is possible, waste wood can be reused, and a molded article made of a mixed material with wood flour is also demanded from an environmental problem. Further, in order to use a molded article having a woody feeling as synthetic wood, it is preferable that cutting and cutting can be performed in the same manner as wood. The reason for this is that if the molded body can be further processed after the production to obtain another shape, the applications will be expanded.

Until now, there has been no known method for producing a norbornene-based resin molded article having a woody feel and capable of being cut or cut in the same manner as wood. Further, it has not been known what kind of wood powder should be used to obtain such a norbornene-based resin molded product.

In the case of a thermoplastic resin, a technique of melting and kneading the resin and wood flour has been put to practical use. In order to melt-knead the resin and the wood flour, it is necessary to maintain the temperature high enough to melt the thermoplastic resin for a long time. If the wood flour contains a certain amount of moisture, the moisture evaporates during melt-kneading or molding, and the molded body foams,
Wood flour is required to contain almost no water. For example, Japanese Patent Application Laid-Open No. Hei 8-100886 discloses a technique in which a polyolefin (thermoplastic resin) and wood flour are melted and kneaded, but the wood flour has a water content of at most 0.8%, preferably at most 0.8%. It is disclosed that the content should be 0.5% or less. However, this knowledge cannot be applied to the reaction molding method based on bulk polymerization because the wood powder is not melt-kneaded.

It has been proposed to use a filler having a low water content in the method for producing a norbornene-based resin molded article by bulk polymerization (JP-A-11-322903).
No.). In this publication, the metathesis catalyst is limited to a specific Ru-based catalyst, and the water content of the various fillers is 0.01 to 0.3% by weight, and the amount of the filler is 100 parts by weight of the norbornene-based monomer. 0.1 to 30 in ratio
It is disclosed that it should be 0 parts by weight (99.9 / 0.01 to 25/75 when the ratio of the norbornene-based monomer to the wood flour is converted to the weight ratio). Wood flour is disclosed as one of the fillers that can be used, but actually trying to handle wood powder with low moisture in this way requires a drying process and management in a state with low moisture, resulting in increased productivity. In addition, there is a problem that the dry wood powder is liable to cause a dust explosion. Further, the publication does not disclose or suggest the texture and workability of the norbornene-based resin molded product.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for safely producing a norbornene-based resin molded product having a woody feel and capable of being cut or cut in the same manner as wood with good productivity. An object of the present invention is to provide a synthetic wood obtained by such a manufacturing method.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above-mentioned object, and as a result, have found that thermoplastic resins and conventional norbornene-based resin molded articles by bulk polymerization have been used. Unlike the knowledge that was considered as common sense, it is important for the purpose of the present invention to use wood flour containing an appropriate ratio of water as a filler,
In other words, by using wood flour containing an appropriate ratio of water as a filler, a norbornene-based resin molded body having a woody feel and capable of being cut and cut in the same manner as wood can be manufactured with good productivity and safety. They found what they could do and completed the present invention.

In order to obtain a norbornene-based resin molded article which has a woody feel and can be cut or cut in the same manner as wood, it is necessary that the ratio of the norbornene-based monomer to wood powder 80/20 to 20/80 by weight
Was found to be preferable.

In order to obtain a norbornene-based resin molded product having a woody feel and capable of being cut or cut in the same manner as wood, with good productivity, the present inventors have proposed a ruthenium complex as the metathesis catalyst. It has been found preferable to use it. Then, by using a ruthenium complex as a metathesis catalyst and adjusting the ratio of the norbornene-based monomer to the wood flour to 80/20 to 20/80 by weight, synthetic wood excellent in woody feel and workability such as cutting and cutting. Was obtained.

Thus, according to the present invention, there is provided a method for producing a norbornene-based resin molded article in which a norbornene-based monomer is bulk-polymerized in the presence of wood powder containing 0.5 to 20% of water using a metathesis catalyst. You.

According to the present invention, the ratio between the norbornene monomer and the wood flour is 80/20 to 20/8 by weight.
And 0 is a method for producing the norbornene-based resin molded article. Further, according to the present invention, there is provided the method for producing a norbornene-based resin molded article, wherein the metathesis catalyst is a ruthenium complex. According to the present invention, a norbornene-based resin molded product obtained by bulk polymerization of a norbornene-based monomer in the presence of wood flour containing 0.5 to 20% of water by a ruthenium complex, comprising a norbornene-based monomer and 80/20 to 20/8 in weight ratio with wood flour
Synthetic wood that is zero is also provided.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION (Norbornene-Based Monomer) The norbornene-based monomer that can be used in the present invention is a bicyclic or tri- or more polycyclic hydrocarbon compound having a norbornene ring structure (hereinafter also referred to as norbornenes). And may have a substituent.

Specific examples thereof include norbornene, norbornadiene, methyl norbornene, dimethyl norbornene, ethyl norbornene, chlorinated norbornene, ethylidene norbornene, chloromethyl norbornene, trimethylsilyl norbornene, phenyl norbornene, cyano norbornene, dicyanorbornene, methoxycarbonyl norbornene, and pyridyl. Bicyclic norbornenes such as norbornene, norbornene anhydride, norbornene imide and the like;

Tricyclic norbornenes such as dicyclopentadiene (a dimer of cyclopentadiene), dihydrodicyclopentadiene and its alkyl, alkenyl, alkylidene or aryl substituents; dimethanohexahydronaphthalene, dimethanooctahydronaphthalene and the like; Tetracyclic norbornenes such as alkyl, alkenyl, alkylidene or aryl substituents; pentacyclic norbornenes such as tricyclopentadiene (trimer of cyclopentadiene); hexacyclic norbornenes such as hexacycloheptadecene; dinorbornene And a compound containing a norbornene ring such as an alkyl- or aryl-substituted product thereof.

Co- (bulk) polymerization can also be carried out by using a monocyclic cycloolefin such as cyclobutene, cyclopentene, cyclooctene and cyclododecene and a derivative thereof having a substituent in combination with the norbornene-based monomer.

The norbornene monomers may be used alone or as a mixture of two or more. When two or more kinds are used, a norbornene-based monomer having one double bond to be a thermoplastic resin and a norbornene-based monomer having a plurality of double bonds to be a thermosetting resin are appropriately combined with each other to obtain various A norbornene-based resin molded article having physical properties can be obtained. Also, compared with the case where the norbornene-based monomer is used alone, when two or more kinds are used in combination, there is an advantage at the time of bulk polymerization that a monomer having a high freezing point temperature can be handled as a liquid due to a drop in freezing point.

Of these norbornene monomers, dicyclopentadiene is preferably used as a main component, and more preferably 80% by weight or more is dicyclopentadiene. This is because dicyclopentadiene has excellent activity during bulk polymerization and the resulting norbornene-based resin molded article has high heat resistance. In the norbornene-based monomer, dicyclopentadiene may be pure (for example, 99% by weight or more), and the obtained norbornene-based resin molded article has excellent mechanical strength. % May be included.

(Wood flour) In the present invention, the water content is 0.5 to 20%.
% Wood flour is used. Wood flour is a crushed plant fiber, and its type is not particularly limited. Specific examples of wood flour include wood, rice husk, and pericarp that are finely ground as necessary. Examples of the wood include cedars such as cedar and red cedar; cypress; pine such as red pine; lumber such as oak; and thinned wood such as beech and oak; and waste buildings, furniture, and transportation. It is also preferable to reuse wood such as containers (containers, barrels, pallets, etc.).
Examples of the rice hulls include rice husks such as rice and wheat. Examples of the peel include nut shells such as walnut and almond. Wood flour may be obtained as a material generated during cutting and cutting of wood, or may be obtained by finely pulverizing wood, rice husk, or pericarp using a pulverizer such as a turbo mill as needed.

The water content of the wood flour used in the present invention is 0.1.
It is 5 to 20%, preferably 0.8 to 15%, particularly preferably 1 to 10%. If the amount is too small, the production process of the norbornene-based resin molded body requires a drying step, thereby lowering the production efficiency and increasing the risk of explosion of the excessively dried wood flour. When the water content is within this range, the resulting norbornene-based resin molded product has an excellent woody feel and a good balance of workability such as cutting and cutting. Ordinary timber generally contains a few percent of water and can be used as it is simply by grinding it. If the water content of the wood flour is too low, add water by spraying, etc.
If the amount is too large, the content of water can be adjusted by drying with a blow dryer or the like. The water content is measured as a loss on heating by drying the wood flour at 150 ° C. for 1 hour in a hot air dryer.

The grain size of the wood flour is not particularly limited. The size of the grain (average of the length in the longitudinal direction and the width in the transverse direction when the grain is viewed three-dimensionally) is usually 0.001 to 10 mm,
Preferably 0.01-5 mm, particularly preferably 0.02
３3 mm. When the grain size of the wood flour is in this range, the wood texture of the obtained norbornene-based resin molded article is excellent, and the balance of workability such as cutting and cutting becomes good. The particle size of the wood flour may be used uniformly, or a mixture of large to small particle sizes may be used. In order to make the particle size of the wood flour uniform, it may be classified by a sieve as needed.

The bulk specific gravity of the wood flour is not particularly limited. The bulk specific gravity is usually 0.1 to 0.5 g / cc, preferably 0.1 to 0.5 g / cc.
0.3 g / cc, particularly preferably 0.12 to 0.25
g / cc. When the bulk specific gravity of wood flour is in this range,
The resulting norbornene-based resin molded article has an excellent woody feel and a good balance of workability such as cutting and cutting. Bulk specific gravity is measured as the ratio of wood flour by placing an appropriate amount of wood flour in a graduated cylinder and measuring weight and volume without applying any weight.

The ratio of the norbornene-based monomer to the wood flour is not particularly limited, but is preferably 80/20 to 20/80, and more preferably 70/30 to 50/50 by weight ratio of the norbornene-based monomer to the wood flour. Particularly preferred. When the ratio of norbornene-based monomer and wood flour is in this range,
The resulting norbornene-based resin molded article has an excellent woody feel and a good balance of workability such as cutting and cutting.

(Metathesis Catalyst) The catalyst used in the bulk polymerization of the present invention is not particularly limited as long as it is a metathesis catalyst capable of ring-opening polymerization of a norbornene-based monomer. A metathesis catalyst is a complex in which a plurality of ions, atoms, polyatomic ions, and / or compounds are bonded with a transition metal atom as a central atom. As the transition metal atom, an atom belonging to Group 5, Group 6, or Group 8 (Long Periodic Table, the same applies hereinafter) is used. The atoms of each group are not particularly limited, but examples of the group 5 atoms include tantalum, examples of the group 6 atoms include molybdenum and tungsten, and examples of the group 8 atoms include ruthenium and osmium. No.

For the purpose of the present invention, it is preferred to use a ruthenium or osmium complex of group 8 as a metathesis catalyst, and a ruthenium complex is particularly preferred. Because the activity of the catalyst during the bulk polymerization is excellent, the productivity of the norbornene-based resin molded product is excellent, the odor of the obtained norbornene-based resin molded product (derived from unreacted norbornene-based monomer) is small, and the wood texture is excellent. It is.

Hereinafter, the metathesis catalyst of the present invention includes:
A ruthenium complex in which a plurality of ions, atoms, polyatomic ions and / or compounds are bonded with ruthenium as a central atom is preferred, and a complex in which at least one heteroatom-containing carbene compound is bonded to ruthenium is particularly preferred. .

Specifically, for example, a ruthenium complex represented by the following general formula 1 or 2 may be mentioned.

[0028]

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(R ¹ and R 2 in the formulas ¹ and ² are each independently a hydrogen or a C ₁ -C ₂₀ which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom. Represents a hydrocarbon group, X ¹ and X ²
Each independently represents an anionic ligand. L ¹
Represents a hetero atom-containing carbene compounds, L ² is a hetero atom-containing carbene compound or an electron donor compound any neutral. R ¹ , R ² , X ¹ , X ² , L ¹ and L ²
2, 3, 4, 5, or 6 may combine with each other to form a polydentate chelating ligand. )

In the present invention, the hetero atom refers to an atom belonging to group 15 or 16 of the long-period periodic table, and specifically includes N, O, P, S, As, Se atoms and the like. Can be. Among them, N, O, P and S atoms are preferable for obtaining a stable carbene compound, and N atom is particularly preferable.

The carbene compound is a general term for compounds having a methylene free radical, and refers to a compound having an uncharged divalent carbon atom represented by (> C: also referred to as carbene carbon). It is. Generally, a carbene compound exists as an unstable intermediate generated during a chemical reaction, but can be isolated as a relatively stable carbene compound having a hetero atom.

In the carbene compound of the present invention, it is preferable that a hetero atom is bonded to the carbene carbon, preferably on both sides thereof. Among such carbene compounds, those having a heterocyclic ring containing a carbene carbon atom and heteroatoms on both sides thereof are preferable, and the heterocyclic ring has a saturated ring structure containing no double bond. Particularly preferred. The heteroatom adjacent to the carbene carbon preferably has a bulky substituent. When a metathesis catalyst having a carbene compound having a preferred structure as described above is used, the activity of the bulk polymerization is particularly high, and a post-heating step after the bulk polymerization becomes unnecessary, and the production efficiency of the norbornene-based resin molded article is improved. Become.

Examples of preferred heteroatom-containing carbene compounds in the present invention include the following general formula 3 (1,3-disubstituted imidazolidine-2-ylidenes) or general formula 4
(1,3-disubstituted-4-imidazoline-2-ylidene)
The compound shown by these can be mentioned. The compounds represented by the general formulas 3 and 4 have a hetero ring in which a hetero atom is bonded to both sides of a carbene carbon atom, and the compound represented by the general formula 3 has a hetero ring having a saturated ring structure. Equation 4
Has a ring structure in which the heterocycle contains a double bond.

[0034]

Embedded image

(R ³ and R ⁴ in the above formulas 3 and 4 each independently represent hydrogen or a C ₁ -C ₂₀ which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom. Represents a hydrocarbon group.)

Examples of preferred heteroatom-containing carbene compounds other than the general formulas 3 and 4 include 1,3,4,5-
Tetrasubstituted imidazolidine-2-ylidenes, 1,3,4
5-tetrasubstituted-4-imidazoline-2-ylidenes, 1,
3,4-trisubstituted-2,3,4,5-tetrahydro-1H
-1,2,4-triazole-5-ylidenes, 3-substituted-2,3,4,5-tetrahydrothiazol-2-ylidenes, 1,3-disubstituted hexahydropyrimidine-2
-Ylidene-N, N, N ', N'-tetrasubstituted formamidinylidenes and 3-substituted-2,3-dihydrothiazole-
2-ylidenes and the like can be mentioned. All of these compounds have a structure in which hetero atoms are bonded to both sides of a carbene carbon atom to form a hetero ring,
Preferred of these compounds are those having a structure in which a bulky substituent is bonded to a heteroatom adjacent to the carbene carbon.

[0037] As R ³ and R ⁴ in the general formula 3 and 4, and Examples of the substituent bonded to a hetero atom adjacent to the carbene carbon of the hetero atom-containing carbene compound, bulky group. The bulky group is a group bonded to a hetero atom through a secondary or tertiary carbon, and a group having a carbon-containing ring structure and bonding from carbon in the ring structure to a hetero atom. Specific examples of the bulky group include alkyl groups having a branched structure such as isopropyl and tertiary butyl; alicyclic groups such as cyclohexyl and adamantyl; phenyl, methylphenyl, methylnaphthyl, 2,6-diisopropylphenyl and mesityl. Examples include a substituted or unsubstituted aromatic ring group. When there are a plurality of bulky groups, they may be the same or different from each other in one molecule of the heteroatom-containing carbene compound, and they may be the same (single compound) between different molecules. Or different (mixture).

The anionic (anionic) ligands X ¹ and X ² in the general formulas 1 and 2 may be any ligands having a negative charge when separated from the central metal. Good. For example, halogen atoms such as F, Br, Cl and I; hydrogen; linear, branched or cyclic, substituted or unsubstituted hydrocarbons such as alkyl groups, alkenyl groups, substituted allyl groups and substituted cyclopentadienyl groups. An aromatic hydrocarbon group such as an aryl group; a hydrocarbon group containing an oxygen atom such as an acetylacetonato group, a diketonate group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group or a carboxyl group; an alkylthio group, an alkenylthio group, A hydrocarbon group containing a sulfur atom such as an arylthio group; and a hydrocarbon group containing an oxygen atom and a sulfur atom such as an alkylsulfonate group, an arylsulfonate group, an alkylsulfonyl group and an alkylsulfinyl group. . Preferably it is a halogen atom, more preferably a chlorine atom.

[0039] Formula 1 and the electron donor compound neutral usable in the general formula 2 as L ² is a ligand having a neutral charge when separated from the central metal, i.e. any if Lewis base It may be something. Specific examples thereof include oxygen; water; aromatic compounds, substituted or unsubstituted unsaturated hydrocarbon compounds such as cyclic diolefins and olefins, and oxygen atoms such as ethers, carbonyls and esters. Hydrocarbon compounds; hydrocarbons containing nitrogen atoms such as amides, amines and pyridines; hydrocarbons containing oxygen and nitrogen atoms such as nitriles and isocyanides; phosphines, phosphinites and phosphites Hydrocarbons containing an oxygen atom and a sulfur atom such as sulfoxides and thioethers; compounds containing a nitrogen atom and a sulfur atom such as thiocyanates; stibine And a Lewis base such as a compound containing an antimony atom. Preferred are phosphines, and particularly preferred are trisubstituted phosphines such as trialkylphosphines and triarylphosphines.

R ¹ and R ² in the general formulas 1 and ² are
Independently of one another hydrogen or halogen atom, a hydrocarbon group of oxygen atom, nitrogen atom, sulfur atom, may contain a phosphorus atom or a silicon atom C ₁ -C _20. In particular,
Hydrogen and a C _{2 to} C ₂₀ alkenyl group, an alkynyl group,
Examples thereof include an alkyl group, an aryl group, a carboxyl group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, and an alkylsulfinyl group.

Specific examples of the preferred complex represented by the general formula 1 include (1,3-dicyclohexylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride and (1,3-dicyclohexyl-4-imidazoline). -2-ylidene)
(Tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dimesitylimidazolidine-2-ylidene) (tri Phenylphosphine) benzylidene ruthenium dichloride, (1,3
-Dimesityl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dimesityl-4-imidazoline-2-ylidene) (triphenylphosphine) benzylidene ruthenium dichloride, [1,3-diene (Methylphenyl) imidazolidine-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (methylnaphthyl) imidazolidine-
2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3,4,5-tetraphenylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dicyclohexylhexahydropyrimidine- Ruthenium complex in which a heteroatom-containing carbene compound such as 2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride and a neutral electron-donating compound are coordinated; bis (1,3-diisopropylimidazolidin-2-ylidene) benzylidene ruthenium Dichloride, bis (1,3-dicyclohexylimidazolidin-2-ylidene) benzylidene ruthenium dichloride, bis (1,3-diisopropyl-4-imidazoline-2-ylidene) Benzylidene ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazolin-2-ylidene) including two ruthenium complex hetero atom-containing carbene compound is coordinated such benzylidene ruthenium dichloride.

Further, the complex represented by the above formula 1 or 2 is converted to di-μ-chlorobis [(p-cymene) chlororuthenium], di-μ-chlorobis [(p-cymene) chloroosmium], dichloro (pentane). A dinuclear ruthenium complex obtained by reacting with a dinuclear metal complex such as methylcyclopentadienyl) rhodium dimer may be used.

When the ruthenium complex is used as the metathesis catalyst, the amount used is usually 1: as the molar ratio of the metal ruthenium / norbornene monomer in the ruthenium complex.
2,000 to 1: 2,000,000, preferably 1:
5,000 to 1,000,000, more preferably 1:
10,000 to 1: 500,000. If it is too small, the activity at the time of bulk polymerization is not sufficient, and if it is too large, the activity of the bulk polymerization is too high, which tends to cause reaction unevenness and insufficient filling of the mold.

The metathesis catalyst, which is a ruthenium complex, can be used by dissolving it in a small amount of an inert solvent, if necessary. Examples of the inert solvent include chain aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane Alicyclic hydrocarbon solvents such as tricyclodecane, hexahydroindenecyclohexane and cyclooctane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene and acetonitrile; diethyl ether And ether solvents such as tetrahydrofuran. Further, as long as the activity of the ruthenium complex as a metathesis catalyst is not reduced, a liquid antioxidant, a plasticizer or an elastomer may be used as the solvent. Among these solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents and alicyclic hydrocarbon solvents that are widely used in industry are preferable.

Other metathesis catalysts include complexes of Group 5 and 6 transition metal atoms. When a complex of these transition metal atoms is used as a metathesis catalyst, a halide, an oxyhalide, an oxide,
Used as a complex such as an organic ammonium salt. The amount used is usually in the range of about 0.01 to 50 mmol, preferably 0.1 to 20 mmol, per 1 mol of the norbornene monomer.

When a complex of a transition metal atom of Group 5 or 6 is used as the metathesis catalyst, it is preferable to use it in combination with an activator (cocatalyst) for the purpose of controlling the polymerization activity. The activator is an organoaluminum compound or an organotin compound, specifically, of aluminum and tin,
Examples thereof include (partially) alkylated compounds, (partially) halides, (partially) alkoxylated compounds, (partially) aryloxy compounds, and the like (here, "part" means that a plurality of compounds may be simultaneously formed). The activator is preferably 1 to 10 (molar ratio) based on the metathesis catalyst component.
Use within the range.

When a complex of a transition metal atom belonging to Group 5 or 6 is used as the metathesis catalyst, it is preferable that both the metathesis catalyst and the activator be dissolved in a monomer, but the nature of the product is essential. It may be used by suspending or dissolving it in a small amount of a solvent within a range that does not impair the properties.

(Other Components) In the present invention, a norbornene-based monomer is bulk-polymerized together with wood flour in the presence of a metathesis catalyst. In addition to these components, other components are added within a range not to impair the object of the present invention. In addition, bulk polymerization may be performed.

In the production method of the present invention, if the bulk polymerization reaction starts before the wood flour and the norbornene-based monomer are in a uniform mixed state, the resulting norbornene-based resin molded article becomes inhomogeneous or hardened. It is also preferable to use a component (retarder) for delaying the start of bulk polymerization, since this may cause a failure. Specific examples of such a retarder include Lewis base compounds containing a phosphorus atom such as tricyclopentylphosphine, tricyclohexylhexylphosphine, triphenylphosphine, triphenylphosphite, and n-butylphosphine. In which R ⁵ CH ₂ PR ⁶ R such as n-butylphosphine;
⁷ (R ⁵ , R ⁶ , R ⁷ are an alkyl group, an aryl group, etc.)
The compound represented by is particularly preferable. Examples of different retarders include Lewis base compounds containing a nitrogen atom such as n-butylamine, pyridine, 4-vinylpyridine, acetonitrile, ethylenediamine, N-benzylidenemethylamine, pyrazine, piperidine, imidazole, among these. In this case, a primary amine such as n-butylamine is preferred. Examples of further different retarders include olefin compounds such as vinyl norbornene, propenyl norbornene, isopropenyl norbornene. The amount of the various retarders to be added is preferably 0.1 to 1 mol per 1 mol of the metathesis catalyst (transition metal atom).
The ratio is 1000 mol.

During the bulk polymerization, for example, a colorant, a flame retardant,
Inorganic substances such as a stiffening agent, a low thermal expansion agent, a bulking agent, a lightening agent, a conductivity imparting agent and an antistatic agent can be added. With these inorganic substances, it is also possible to obtain a norbornene-based resin molded article having a tactile sensation like wood and having a color tone different from that of wood.

During the bulk polymerization, various organic substances such as a flame retardant and an impact modifier can be added. Also, for the purpose of improving the mechanical strength of the obtained norbornene-based resin molded article, for example, fine particles such as silicone resin, polyamide resin, polyester resin, polyphenylene oxide, polyphenylene sulfide, and phenolic thermosetting resin; aramid fiber; A single fiber chop such as polyamide fiber or polyester fiber may be added.

In addition to improving the impact resistance of the resulting norbornene-based resin molded article, various elastomers can be added during bulk polymerization for the purpose of adjusting the viscosity of the norbornene-based monomer. Examples of the elastomer include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), and ethylene. -Propylene-diene terpolymer (EPDM),
Examples include ethylene-vinyl acetate copolymer (EVA) and hydrides thereof. Among them, those having a styrene skeleton or a butadiene skeleton are particularly preferable. The elastomer is usually used by dissolving it in a reaction solution containing a norbornene-based monomer in advance. By dissolving the elastomer, when the reaction solution containing the monomer has a low viscosity, the viscosity can be adjusted to an appropriate one. The amount of the elastomer used is usually 0.5 part with respect to 100 parts by weight of the obtained polynorbornene-based resin.
-20 parts by weight, preferably 1-15 parts by weight, more preferably 2-10 parts by weight. If the amount of the elastomer is too small, the effect of imparting impact resistance to the obtained norbornene-based resin molded article is small, and if it is too large, the viscosity of the reaction solution becomes too high, and the operability during bulk polymerization deteriorates. Also, the heat deformation temperature and flexural modulus of the obtained norbornene-based resin molded article tend to decrease.

Further, it is preferable to add a soluble antioxidant to the norbornene-based monomer in order to improve the storage stability of the norbornene-based monomer.
In addition, in order to improve the storage stability and weather resistance of the obtained norbornene-based resin molded product, an antioxidant soluble in the norbornene-based monomer, an ultraviolet absorber and a weather-resistant stabilizer additive are added to the norbornene-based monomer in advance. It is also preferred to add or add by the time of bulk polymerization of the reactive mixture. Examples of the antioxidant and the weather resistance stabilizer include a hindered phenol-based antioxidant and a phosphorus-based antioxidant. Among the antioxidants, hindered phenolic antioxidants are preferred because of their excellent effects. Examples of such hindered phenolic antioxidants include 2,6-di-t-
Butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate, tetrakis- [methylene-3- (3 ', 5'-
Di-tert-butyl-4'-hydroxyphenyl) propionate] methane, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) ), 4,
4'-methylenebis (2,6-di-t-butylpheno-
1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene, 1,3,5-tris (3 ′, 5′-di-t-
(Butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione and the like. Various oil-soluble dyes can be used as the ultraviolet absorber. The addition amount of the antioxidant, weather stabilizer and ultraviolet absorber is usually 50 to 10,000 ppm or less, but may be added in excess of 10,000 ppm.

(Bulk Polymerization) The method for producing a norbornene-based resin molded article of the present invention is a bulk polymerization of a norbornene-based monomer. However, by using a metathesis catalyst, a mixture of a liquid norbornene-based monomer and wood powder can be prepared at once. Thus, a norbornene-based resin molded article can be obtained. This bulk polymerization reaction is rapid, and when a preferable ruthenium complex complex is used as a metathesis catalyst, the temperature of the polymerization reaction has a large temperature dependence. The temperature rises extremely fast, and as a result, the temperature rise (heat rise curve) at the time of heat generation becomes steep. The maximum heating rate is usually 10 ° C./sec or more.

The molding apparatus and molding method used in the method for producing a norbornene-based resin molded article of the present invention are not particularly limited. The method of performing bulk polymerization in the inside is useful. The mold is used to obtain a molded product having a predetermined shape. In such bulk polymerization, a molding machine conventionally known as an RTM machine or a RIM machine can be used. The mold used in these molding methods may be a mold having a split mold structure, that is, a mold having a core mold and a cavity mold, or a mold having a structure in which an upper surface is opened.

As a molding method, a hand lay-up (manual molding) method can also be preferably used. In this molding method, a mold generally has a structure in which an upper surface is opened.

As a molding method, a reactive extrusion molding method (a molding method in which the reactive mixture is continuously supplied under pressure into a mold by a screw and the reactive mixture is continuously polymerized in a mold in a bulk) is also preferably used. be able to. According to the reaction extrusion molding method, while extruding from an appropriate die while mixing each component with a screw in an extruder, a norbornene-based resin molded product such as a log, a square or a cylinder is continuously obtained. This is particularly preferable as a method for obtaining the synthetic wood of the present invention. Reactive pultrusion molding method (JP-A-2
000-290382) can be preferably used because a molded article having a similar shape can be obtained.

The order of mixing the essential components of the metathesis catalyst, the norbornene-based monomer and the wood flour is not particularly limited, but the metathesis catalyst and, if necessary, the cocatalyst and the norbornene-based monomer are uniformly mixed to obtain a reactive mixture. It is preferable to uniformly mix the reactive mixture with the wood flour after the mixture is formed and before the bulk polymerization starts and the viscosity sharply increases. For the preparation of the reactive mixture, a known stirrer, homogenizer, static mixer or collision mixer can be used. Whether or not each of the mixed states has become uniform is visually confirmed, for example. By adopting such an order, the obtained norbornene-based resin molded product becomes homogeneous, and hardening failure is less likely to occur, which is preferable. When a mold having an open top surface is used, such as in a hand lay-up method, it is also preferable that the step of uniformly mixing the reactive mixture and wood flour be performed in the mold. The step of mixing other components is not particularly limited.For example, components that can be dissolved in the norbornene-based monomer are mixed with wood flour before the preparation of the reactive mixture. It is also preferable to keep it.

The temperature of the norbornene-based monomer or the reactive mixture and the wood flour before the start of the bulk polymerization reaction is not particularly limited, and may be room temperature (about 20 ° C.), or 20 to 20 to increase the activity of the bulk polymerization. The temperature may be raised between 80 ° C. However, in the method for producing a norbornene-based resin of the present invention, if the bulk polymerization reaction starts before the wood flour and the norbornene-based monomer are in a uniform mixed state, the obtained norbornene-based resin molded article may be heterogeneous. Depending on the molding method, it is also preferable to cool the norbornene-based monomer or the reactive mixture to room temperature or lower in order to delay the start of the bulk polymerization, since this may result in poor curing. The temperature for cooling is, for example, in the range of −20 to 20 ° C.

When the wood flour is mixed with the norbornene-based monomer or the reactive mixture, it is difficult to mix the wood flour due to its low bulk density. In order to mix them, it is necessary to sufficiently mix them with a mixer suitable for mixing insoluble solids such as a known rotary stirrer or static mixer. The time required for the mixing must be performed before the bulk polymerization reaction starts and the viscosity of the reactive mixture starts to increase. A method of simultaneously performing mixing and molding by a screw of an extruder is also conceivable.

After mixing the norbornene-based monomer and the metathesis catalyst, the bulk polymerization usually starts within a few minutes, the temperature rises, and the polymerization reaction proceeds.

(Norbornene-Based Resin Molded Article and Synthetic Wood) In the case of a mold having a split mold structure, a mold having a split mold structure can be obtained by opening the mold after cooling for a certain period of time, if necessary, after the completion of bulk polymerization. Can be In the case of a top-opening mold, it can be obtained by taking out from the mold after cooling for a certain period of time, if necessary, after completion of the bulk polymerization. In the case of the reaction extrusion molding method or the reaction pultrusion molding method, a norbornene-based resin molded product is continuously obtained from a die.

The norbornene-based resin molded product obtained by the method of the present invention has a woody feel as it is, and can be cut or cut in the same manner as wood, and can be used as synthetic wood. Further, the surface of the norbornene-based resin molded product may be colored or transparently coated to obtain synthetic wood. The paint used for the colored coating or the transparent coating may contain various ultraviolet absorbers, weather stabilizers and anti-aging agents for the purpose of improving the weather stability of the norbornene-based resin molded article.

[0064]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples below, but the present invention is not limited to these examples. Unless otherwise specified, parts and percentages are by weight.

Example 1 In a 500 ml reactor equipped with a rotary stirrer having a plurality of stirring blades, 75 g of dicyclopentadiene (containing about 10% of cyclopentadiene trimer) as a norbornene-based monomer was placed. , Liquid temperature is 1
Cooled to 0 ° C. in an ice bath. Benzylidene (1,3-dimesitylimidazolidine-2) as a metathesis catalyst
-Ylidene) (tricyclohexylphosphine) ruthenium dichloride (Org. Lett. 1999, 1
Synthesized based on the description in Vol. 953) 46.5
mg of toluene dissolved in 2.7 ml of toluene (ruthenium complex / norbornene monomer = 1 / 10,000 (mo)
1 / mol)) was added to the above reactor to form a reactive mixture (time 0 sec), and the mixture was stirred with a stirrer until the mixture became visually uniform. Wood powder (cedar wood was crushed by a turbo mill, water content was 7.3%, and grain size was 0.1 mm.
50 g of 1 mm, bulk specific gravity 0.18 g / cc) was added to the above reactor (weight ratio of norbornene monomer / wood flour 6).
0/40), the mixture was visually stirred using a stirrer until the mixture became uniform, and then the stirrer was removed. The time when the mixing of the wood flour was completed was 90 seconds. As a mold, the bottom is 100mm ×
Prepare a 100 mm square SUS container and quickly pour the contents of the reactor into the SUS container.
A plate-shaped lid of 00 mm x 100 mm was placed (the lid was not a closed structure but provided with an appropriate vent gap), and was held down by a 10 kg weight. At about 200 seconds, the temperature starts to rise,
The polymerization reaction started and then ended. After the completion of the polymerization reaction, the mold was left at room temperature, and was taken out after the mold was sufficiently cooled.

The obtained norbornene-based resin molded product (test piece 1) had a size of 100 mm × 100 mm × thickness 15 mm, and had the same texture and appearance (woody texture) as wood when touched by hand. Was something. When the odor of the test piece 1 was smelled, it was found that there was almost no odor, the bulk polymerization proceeded uniformly, and there was no site where poor curing occurred. When the appearance was confirmed, no trace of foaming was observed on the surface of the molded product, and no large unevenness was found on the surface. When specimen 1 was cut into two pieces of almost the same size with a woodworking saw,
The saw tooth and the test piece 1 could be processed like wood without fusing. When a 10M hole was drilled in each of the two cut test pieces (test piece 1A and test piece 1B) with a woodworking drill, they could be processed in the same manner as wood.
Although the cut surface and the wall surface of the hole were confirmed, there was no void-shaped void.

The holes of the test piece 1A and the test piece 1B were overlapped, and 8
The two test pieces were fitted using an M bolt nut and a washer. In this state, the plate was left at room temperature for 30 days, but no cracks or the like were formed around the hole of the bolt.

(Example 2) The same wood flour as used in Example 1 was dried with a hot air drier at 80 ° C for 20 minutes to obtain wood flour having a moisture content of 2.5%. A test piece 2 was obtained in the same manner as in Example 1 except that 40 g of this wood flour (weight ratio of norbornene-based monomer / wood flour was 65.2 / 34.8) was used.

The test piece 2 had a size of 100 mm × 100 mm × thickness of 14 mm and had a woody feeling. When the odor of the test piece 2 was smelled, it was found that there was almost no odor, the bulk polymerization proceeded uniformly, and there was no site where poor curing occurred. When the appearance was confirmed, no trace of foaming was observed on the surface of the molded product, and no large unevenness was found on the surface. When the test piece 2 was cut into two pieces of approximately the same size with a woodworking saw, the saw teeth and the test piece 2 could be processed in the same manner as wood without fusing. When a 2.5M hole was drilled with a wood drill in both test pieces (test piece 2A and test piece 2B) cut into two pieces, they could be processed in the same manner as wood. The cut surface was confirmed, but there was no void-shaped void.

The holes of the test piece 2A and the test piece 2B were overlapped with each other, and the two test pieces were fitted using a corsed thread (wood screw having a small taper). In this state, it was left at room temperature for 30 days, but no cracks or the like were formed around the hole.

The norbornene-based resin molded product obtained as described above had a woody appearance and was free from irregularities on the surface and molding defects on the surface and inside. The obtained norbornene-based resin molded product could be processed in the same manner as wood, such as various cutting processes and screwing.

[0072]

The norbornene-based resin molded product obtained by the method of the present invention has a woody feel and is free from irregularities on the surface and molding defects on the surface and inside. Also,
It can be processed in the same way as wood, such as various cutting processes and screwing. The norbornene-based resin molded product obtained by the method of the present invention is, for example, as synthetic wood, a substitute for wood or an application whose performance is insufficient with wood, such as building materials, construction materials, park materials and transport containers or storage containers. It can be applied as a material.

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 2B260 BA18 DA01 EA12 4F071 AA69 AA73 AC18 AE06 AH03 BA07 BB01 BC03 BC08 BC09 4J002 AH00X CE00W EZ006 FD09X FD146 GG01 GL00 4J032 CA34 CA35 CA36 CA38 CA46 CC18 CB01 CE04

Claims (4)

[Claims] 1. 0.5 to 20% by a metathesis catalyst
A method for producing a norbornene-based resin molded product, comprising subjecting a norbornene-based monomer to bulk polymerization in the presence of wood powder containing water. 2. The production method according to claim 1, wherein the ratio between the norbornene-based monomer and the wood flour is 80/20 to 20/80 by weight. 3. The method according to claim 1, wherein the metathesis catalyst is a ruthenium complex. 4. 0.5 to 20% by a ruthenium complex
A norbornene-based resin molded article obtained by bulk polymerization of a norbornene-based monomer in the presence of wood powder containing water, wherein the ratio of the norbornene-based monomer to the wood flour is 80/20 to 20/80 by weight. Is a synthetic wood.