JP2001064488A - Cycloolefin composition and molded form - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cycloolefin composition excellent in water resistance by including a specific monomer, a filler, a specific coupling agent and a metathesis polymerization catalyst to improve its mechanical properties subject to deteriorate when incorporated with the filler. SOLUTION: This cycloolefin composition is obtained by including (A) 100 pts.wt. of a metathesis-polymerizable cycloolefin monomer, (B) 1-99 pts.wt. of a filler, (C) 0.01-20 pts.wt., based on 100 pts.wt. of the component B, of an alkylsilane coupling agent of the formula (R)n-Si-(R1)4-n (R is an alkyl, at least one of them being >=6C alkyl; R1 is an alkoxy; n is 1-3) and (D) 0.001-5 pts.wt., based on 100 pts.wt. of the component A, of a metathesis polymerization catalyst pref. a catalyst of the formula [M is ruthenium or osmium; X and X1 are each an anionic ligand; L and L1 are each a neutral electron-donating group; Q and Q1 are each H, a (substituted) alkyl, (substituted) alkenyl or (substituted) aromatic group] or the like}.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cycloolefin composition containing a filler, and more particularly, to a composition having improved mechanical properties which are reduced when a filler is added and having excellent water resistance. Further, the present invention relates to a molded article of a cycloolefin composition containing a filler.

[0002]

2. Description of the Related Art It is known that cycloolefins undergo ring-opening polymerization using a metathesis polymerization catalyst system. For example, J. Am. Chem. Soc. , 196
0, Vol. 82, 2337 describe that ring-opening polymerization of norbornene is carried out by a metathesis catalyst system.
gew. Chem. Int. Edn. , 1964, Vo
l.3,723 contains cyclopentene as a metathesis catalyst system [Mo
Cl ₅ / Al (C ₂ H ₅ ) ₃ ]. Further, a method of producing a polymer by ring-opening polymerization of a cycloolefin is also known. For example,
JP-A-50-130900 and JP-A-52-330
No. 00 discloses a method for producing a ring-opening polymer using a metathesis catalyst system comprising a halide such as tungsten or molybdenum and an organoaluminum compound.

On the other hand, there is also known a method in which a norbornene-type monomer such as dicyclopentadiene or tricyclopentadiene is subjected to bulk polymerization by reaction injection molding (RIM) to obtain a crosslinked polymer molded product. For example, JP-A-58-12
No. 7728 and JP-A-58-129003 disclose a solution A comprising a mixture of a catalytic component of a metathesis catalyst system and a monomer, and a solution B comprising a mixture of an activator of a metathesis catalyst system and a monomer. Reaction injection molding (RIM)
To obtain a crosslinked polymer molded product.

JP-A-59-51911 discloses a metathesis catalyst in which a catalyst component selected from organic ammonium salts of tungsten and molybdenum is combined with an activator selected from alkoxyalkylaluminum halides and aryloxyaluminum halides. A method for producing a crosslinked polymer molded article by reaction injection molding of a norbornene-type monomer using the system is disclosed.

[0005] Japanese Patent Application Laid-Open No. 3-205409 discloses a double decomposition in which a catalyst component selected from tungsten hexachloride and tungsten oxytetrachloride is combined with an activator selected from diethyl aluminum chloride and ethyl aluminum dichloride. A method for producing a dicyclopentadiene polymer crosslinked by a reaction injection molding method using a catalyst system is disclosed. It has been found that in these metathesis catalyst systems, the catalyst component is activated by an activator and causes ring-opening polymerization of the norbornene-type monomer. In the case of performing the reaction injection molding, the solution A and the solution B are collision-mixed, and the mixed solution is immediately poured into a mold in a liquid state,
Ring-opening polymerization is performed in bulk. In the metathesis catalyst system described above, it has been found that the catalyst component is activated by a cocatalyst (activator) component and causes ring-opening polymerization of norbornene-type cycloolefins. When the above reaction injection molding is performed, the solution A and the solution B are collision-mixed, and the mixed solution is immediately poured into a mold in a liquid state, and is subjected to ring-opening polymerization in a lump. It is also known that the cured product obtained in this way has excellent mechanical properties, electrical properties, water resistance and the like.

[0006]

The polymer of cycloolefin using these metathesis polymerization catalysts has excellent mechanical properties. For example, it is known that when a bending test is performed, a yield phenomenon is exhibited, the deflection rate is extremely large, and toughness is higher than other thermosetting resins such as an epoxy resin and an unsaturated polyester resin. However, since the compound viscosity increases remarkably when a filler is added, it is known to add various coupling agents to reduce the viscosity and improve the adhesiveness between the resin and the filler. For example, a norbornene-based silane coupling agent as disclosed in Japanese Patent No. 2755642. Allyl silane coupling agents and vinyl silane coupling agents as disclosed in Japanese Patent No. 2859300.
Japanese Patent Application Laid-Open No. 9-183833 discloses a general silane coupling agent. In this case, the elasticity of the polymer increases due to the adhesion between the resin and the filler, and the bending during the bending test also decreases, so that there is a disadvantage that toughness, which is one of the characteristics described above, is lost. . However, if the silane coupling agent is not used, the viscosity of the compound becomes high, and the workability deteriorates. Furthermore, due to the interfacial peeling phenomenon between the filler and the resin, when used for electric parts, the water resistance, the electric insulation, and the like are reduced. An object of the present invention is to provide a composition having improved mechanical properties which are reduced when a filler is added to a cycloolefin composition containing the filler and having excellent water resistance, and to provide an improved molded article thereof.

[0007]

Means for Solving the Problems The present inventors have studied various coupling agents in order to enable a large amount of filler to be added while maintaining the toughness of cycloolefins. As a result, voids at the resin-filler interface are eliminated, and the toughness of the polymer is maintained by the use of an alkylsilane coupling agent that absorbs the distortion of both phases. And completed the present invention.

That is, the present invention relates to a cycloolefin composition containing a filler, and more particularly to a composition having improved mechanical properties which are reduced when a filler is added and having excellent water resistance and the like. The present invention also provides a molded article of a cycloolefin composition containing a filler. The present invention
A cycloolefin composition comprising (a) a metathesis-polymerizable cycloolefin monomer, (b) a filler, (c) an alkylsilane coupling agent represented by the general formula (1), and (d) a metathesis polymerization catalyst. . (A) 100 parts by weight of a metathesis polymerizable cycloolefin monomer, (b) 1 to 99% by weight of a filler based on the total amount of the composition, (c) an alkylsilane cup represented by the general formula (1) The ring agent is used in an amount of 0.01 to 100 parts by weight of the filler.
It is a preferable cycloolefin composition to mix 0.001 to 5 parts by weight of the metathesis polymerization catalyst with respect to 100 parts by weight of the cycloolefin monomer.

[0009]

(R) n -Si- (R ¹ ) 4 -n (1) wherein R represents an alkyl group, at least ^one of which is an alkyl group having 6 or more carbon atoms, and R ¹ is Each independently represents an alkoxy group, wherein n is an integer of 1 to 3]

[0010] Further, the present invention provides a method wherein the metathesis polymerization catalyst comprises:
The above-mentioned cycloolefin composition is preferably a ruthenium compound, and the above-mentioned cycloolefin composition is preferably a metathesis polymerization catalyst represented by the general formula (A).

[0011]

Embedded image (M represents ruthenium or osmium, X and X1 each independently represent an anionic ligand, L and L1 each independently represent a neutral electron donating group, and Q and Q1 each independently represent hydrogen, alkyl Group, alkenyl group or aromatic group, and the alkyl group, alkenyl group or aromatic group may have a substituent.) Further, the metathesis polymerization catalyst is a catalyst represented by the general formula (B). The above-mentioned cycloolefin composition is preferred.

[0012]

Embedded image (M represents ruthenium or osmium, X and X1 each independently represent an anionic ligand, L and L1 each independently represent a neutral electron donating group, and R ¹ and R ² each independently represent a carbon atom. An alkyl group having 1 to 18 carbon atoms, 2 carbon atoms
Alkenyl group having 2 to 18 carbon atoms, alkynyl group having 2 to 18 carbon atoms, aryl group, carboxylate group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, alkenyloxy group having 2 to 18 carbon atoms, 2 carbon atoms -18 alkynyloxy group, C2-C18 allyloxy group, C2-C1
8 alkoxycarbonyl group, an alkylthio group having 1 to 18 carbon atoms, an alkyl sulfinyl group having an alkylsulfonyl group, or 1 to 18 carbon atoms having 1 to 18 carbon atoms, R ³
Represents hydrogen, an aryl group or an alkyl group having 1 to 18 carbon atoms. )

The metathesis polymerization catalyst is the above cycloolefin composition which is preferably a catalyst represented by the general formula (C).

[0014]

Embedded image (M represents ruthenium or osmium, X and X1 each independently represent an anionic ligand, L and L1 each independently represent a neutral electron donating group, and Q and Q1 each independently represent hydrogen, alkyl Group, alkenyl group or aromatic group, and the alkyl group, alkenyl group or aromatic group may have a substituent.)

[0015] The present invention is the above cycloolefin composition, which preferably contains any one of glass, silica, alumina, magnesium hydroxide, aluminum hydroxide, and silica sand as one component of the filler (b). The above cycloolefin composition preferably contains (a) dicyclopentadiene as one of the cycloolefin monomer components. And this invention is a molded object which consists of said cycloolefin composition.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The cycloolefin composition containing a filler used in the present invention comprises (a) a cycloolefin monomer capable of metathesis polymerization, (b) a filler, and (c) a compound represented by the general formula (1). Alkyl silane coupling agent,
(D) It comprises a metathesis polymerization catalyst.

The (a) cycloolefin monomer capable of metathesis polymerization used in the present invention may be any monomer that is useful in metathesis polymerization. Among them, norbornene-type cycloolefins such as substituted or unsubstituted norbornene, dicyclopentadiene, and dihydrodicyclopentadiene are preferably used. Examples of the norbornene-type cycloolefin include bicyclic norbornenes such as norbornene, methylnorbornene, dimethylnorbornene, ethylnorbornene, ethylidene norbornene, and butylnorbornene, dicyclopentadiene (a dimer of cyclopentadiene), dihydrodicyclopentadiene, and methyldicyclone. Tricyclic norbornenes such as pentadiene and dimethyldicyclopentadiene, tetracyclic norbornenes such as tetracyclododecene, methyltetracyclododecene and dimethylcyclotetradodecene, tricyclopentadiene (trimer of cyclopentadiene), tetracyclopentadiene ( Norbornene having five or more rings, such as a tetramer of cyclopentadiene). Further, a compound having two or more norbornene groups, for example, norbornadiene, tetracyclododecadiene, symmetric tricyclopentadiene, or the like can be used as the polyfunctional crosslinking agent.

As other cycloolefins, cyclobutene, cyclopentene, cyclooctene, cyclooctadiene, cyclooctatriene, cyclododecatriene and the like can be used. Further, a dicyclopentadiene-based petroleum resin obtained by thermal polymerization or cationic polymerization of dicyclopentadiene can also be used.
These cycloolefins can be used alone or in combination of two or more. Among them, dicyclopentadiene, methyltetracyclododecene, ethylidene norbornene,
Tricyclopentadiene and tetracyclopentadiene are preferred, and dicyclopentadiene is particularly preferred.

Normal commercially available dicyclopentadiene may contain, as impurities, vinylnorbornene, tetrahydroindene, methylvinylnorbornene, methyltetrahydroindene, methyldicyclopentadiene, dimethyldicyclopentadiene, tricyclopentadiene and the like. Yes, dicyclopentadiene of various purity is commercially available. The dicyclopentadiene used in the present invention has a purity of 80% by weight or more, preferably 90% by weight or more, although it varies depending on the intended use of the obtained polymer.

When dicyclopentadiene is used, a part of the dicyclopentadiene is converted into a cyclopentadiene oligomer such as tricyclopentadiene or tetracyclopentadiene by heating beforehand, or vinylnorbornene or methylvinylnorbornene as an impurity is used. Can be isomerized to tetrahydroindene or methyltetrahydroindene. The heat treatment is usually performed at 120 to 250 ° C. for about 0.5 to 10 hours.

Further, an antioxidant can be added to the cycloolefin monomer used in the present invention, if necessary. Note that ordinary commercially available dicyclopentadiene already contains an antioxidant such as 2,6-di-t-butyl-4-methylphenol and 4-t-butylcatechol. In use, the contained antioxidant can be removed or newly added. The antioxidant to be used is not particularly limited as long as it has an antioxidant ability, and preferred examples include a hindered phenol-based antioxidant, and 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-t-
Butylphenol), 2,2′-methylenebis (4-ethyl-6-t-butylphenol), 4,4′-methylenebis (2,6-di-t-butylphenol),
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. The addition amount of the antioxidant is usually 10 to 10,000 p
pm. As the other antioxidants, the above-mentioned hindered phenol-based amine-based, sulfur-based, phosphorus-based antioxidants and heat deterioration inhibitors can be used alone or in combination of two or more. An absorber, a light stabilizer and the like can be used in combination.

In order to adjust the polymerization reaction, triphenylphosphine, tricyclohexylphosphine,
An appropriate amount of a reaction modifier such as tricyclopentyl phosphine, tributyl phosphine, triisopropyl phosphine (usually 0.0 to 100 parts by weight of the raw material monomer)
01 to 10 parts by weight).

Examples of the filler (b) used in the present invention include the following. These can be used alone or in combination of two or more. Their shape is not particularly limited, such as powder, fiber, and plate. Examples of the oxide-based filler include silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrites. Hydroxide-based fillers include calcium hydroxide, magnesium hydroxide,
Examples include aluminum hydroxide and basic magnesium carbonate. Calcium carbonate as a carbonate-based filler,
Examples include magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, and hydrotalcite. Examples of the sulfate-based filler include calcium sulfate, barium sulfate, and gypsum fiber. Examples of the silicate-based filler include calcium silicate (wollastonite, zonotolite), talc, clay, kaolin, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, serisarito, glass powder, glass fiber, and glass beads. , A glass balloon and the like. Examples of the nitride-based filler include aluminum nitride, boron nitride, and silicon nitride. Examples of the carbon-based filler include carbon black, graphite, carbon fiber, carbon balloon, and charcoal powder. Other fillers include various metal powders, metal fibers, whiskers such as potassium titanate, thermoplastic resin and thermosetting resin powders and fibers, and natural materials such as silica sand, crushed stone, and gravel.

The filler is preferably an oxide, a hydroxide, a carbonate, a sulfate, or a silicate. Further, glass, silica, alumina, magnesium hydroxide, aluminum hydroxide, and silica sand are more preferable.
The amount of the filler added is 1 to the total amount of the composition.
It is from 99 to 99% by weight, preferably from 5 to 95% by weight, more preferably from 30 to 90% by weight.

The (c) alkylsilane coupling agent represented by the general formula (1) used in the present invention is:

[0026]

(R) n -Si- (R ¹ ) 4 -n (1) wherein R represents an alkyl group, at least ^one of which is an alkyl group having 6 or more carbon atoms, and R ¹ represents Independently represents an alkoxy group, wherein n is an integer of 1 to 3.
Examples of the alkyl group having 6 or more carbon atoms include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl. The number of carbon atoms in the alkyl group is 6 or more, preferably 8 or more, more preferably 10 or more. When the number of carbon atoms is smaller than 6, the effect of maintaining toughness is small. In the formula, n represents an integer of 1 to 3, and n is more preferably 2 than 3, and most preferably 1, from the viewpoint of hydrolysis rate. In the formula, R ¹ is independently an alkoxy group,
For example, there are a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group and the isomers thereof, and a methoxy group and an ethoxy group are preferred from the viewpoint of hydrolyzability and ease of handling.

Specific examples of these silane coupling agents include hexyl trimethoxy lan, hexyl triethoxy lan, heptyl trimethoxy lan, octyl trimethoxy lan, octyl triethoxy lan, nonyl trimethoxy lan and nonyl trimethoxy lan. Ethoxylan, decyltrimethoxylan, decyltriethoxylan, dodecyltrimethoxylan, dodecyltriethoxylan, tetradecyltrimethoxylan, tetradecyltriethoxylan, pentadecyltrimethoxylan, pentadecyltriethoxylan and the like.

Also, dialkoxysilanes and monoalkoxysilanes of each silane can be used. Specific examples of these include hexylmethyldimethoxylan, hexylmethyldiethoxylan, heptylmethyldimethoxylan, heptylmethyldimethoxylan, octylmethyldimethoxylan, octylmethyldiethoxylan, nonylmethyldimethoxylan, and nonylmethyldiethoxylan. Orchid, decylmethyldimethoxylan, decylmethyldiethoxylan, dodecylmethyldimethoxylan, dodecylmethyldiethoxylan, tetradecylmethyldimethoxylan, tetradecylmethyldiethoxylan, pentadecylmethyldimethoxylan, pentadecylmethyldiethoxylan, etc. There is.

These coupling agents may be used alone or in combination of two or more. If necessary, other conventionally known silane coupling agents and titanium-based, aluminum-based and zirconium-based coupling agents may be used. It can be used in combination with a metallic coupling agent and a lubricant such as a fatty acid.

As these coupling agents, metal-based coupling agents are preferred, and titanium-based coupling agents are more preferred.
By using a titanium coupling agent together, it is possible to reduce viscosity and improve mechanical properties. Examples of these titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tri-n-dodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, and tetraoctyl bis (ditrityl). (Decyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate,
Bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryloyl isostearyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl Examples include phenyl titanate and isopropyl tri (N-aminoethyl-aminoethyl) titanate.

The amount of the alkylsilane coupling agent (c) used in the present invention is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the filler. The reason is that if the amount used is less than the above ratio, the wettability between the filler and the resin becomes insufficient, and the effect of improving the mechanical properties and the like of the composite material is insufficient. Further, if the amount of the alkylsilane coupling agent used is larger than the above ratio, the mechanical properties and the water resistance are not further improved, which is not preferable from the viewpoint of economy. For the same reason, the amount of the coupling agent such as a titanium-based coupling agent that can be used in combination is 0.0 to 100 parts by weight of the filler.
The amount is preferably 1 to 20 parts by weight, more preferably 0.5 to 5 parts by weight.

The (c) alkylsilane coupling agent used in the present invention may be used after previously treating a filler, or may be used by adding it at the time of mixing the resin and the filler. When the filler is treated in advance, it may be performed by a conventionally known silane coupling agent treatment method. For example, in the case of a powdery filler, the silane coupling agent is added directly or diluted with a solvent, mixed with a stirrer such as a Henschel mixer or a super mixer, and then subjected to a heat treatment. What is necessary is just to make a coupling agent and a filler react. Heating condition is 60
It is preferably carried out at a temperature of from 140 to 140 ° C for 1 to 6 hours. In the case of a fibrous form, the fiber may be immersed in a solution obtained by diluting the silane coupling agent and then treated under the same heating conditions.
When adding a silane coupling agent at the time of mixing the resin and the filler, for example, after adding and dispersing the silane coupling agent in the resin or the filler, the resin and the filler are mixed, and then heated under the same conditions. I just need to do the processing

The (d) metathesis polymerization catalyst used in the present invention is not particularly limited as long as it is a catalyst system known as a catalyst for ring-opening polymerization of a cycloolefin compound.

The catalyst used as the metathesis polymerization catalyst of the present invention is a two-component complex metal halide comprising a transition metal such as titanium, vanadium, molybdenum, tungsten, rhenium, iridium, ruthenium and osmium, metal carbene or Ziegler. It is a Natta-type coordination catalyst. Specific examples include tungsten compounds such as tungsten hexachloride, tungsten oxytetrachloride, tungsten oxide, and tridecyl ammonium tungstate; molybdenum compounds such as molybdenum pentachloride, molybdenum oxytrichloride, molybdenum oxide, and tridecyl ammonium molybdate; Tantalum compounds such as tantalum chloride, [(cyclohexyl) 3P] 2RuCl2, [(phenyl) 3P] 3RuCl2, (cyclohexyl) 3P (p-cymene) RuCl
2, ruthenium compounds such as [(phenyl) 3P] 3 (CO) RuH2.

If necessary, a known cocatalyst (activator) is used in combination with the two-component metathesis polymerization catalyst system. Specific examples thereof include an alkylaluminum halide, an alkoxyalkylaluminum halide, an aryloxyalkylaluminum halide, and an organotin compound.

Next, the one-component type metathesis polymerization catalyst is different from a conventionally known two-component type catalyst system in which a catalyst component and an activator are combined with each other. A catalyst capable of ring-opening polymerization of a cycloolefin compound by a metathesis reaction without easily losing catalytic activity by water.Specifically, a catalyst having a large steric hindrance with a metal carbene structure of ruthenium or osmium as a central skeleton. A metal carbene-type coordination catalyst stabilized with respect to moisture by adopting a structure in which a ligand is coordinated to a central metal is exemplified.

Preferred examples of these ruthenium or osmium metal carbene-type coordination catalysts include compounds represented by the following general formula (A), general formula (B) or general formula (C).

[0038]

Embedded image M represents ruthenium or osmium; X and X1 each independently represent an anionic ligand; L and L1 each independently represent a neutral electron donating group; Q and Q1 each independently represent a hydrogen or alkyl group Alkenyl group or aromatic group, and the alkyl group, alkenyl group or aromatic group may have a substituent.

[0039]

Embedded image M represents ruthenium or osmium; X and X1 each independently represent an anionic ligand; L and L1 each independently represent a neutral electron donating group; Q and Q1 each independently represent a hydrogen or alkyl group Alkenyl group or aromatic group, and the alkyl group, alkenyl group or aromatic group may have a substituent.

Further, more preferable examples in terms of high catalytic activity, high synthesis yield, economical efficiency, and the like include compounds represented by the following general formula (C).

Embedded image M represents ruthenium or osmium, X and X1 each independently represent an anionic ligand, L and L1 each independently represent a neutral electron donating group, and R ¹ and R ² each independently represent a carbon number. Alkyl group of 1 to 18, carbon number of 2
18 alkenyl groups, alkynyl groups having 2 to 18 carbon atoms,
Aryl group, carboxylate group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, alkenyloxy group having 2 to 18 carbon atoms, alkynyloxy group having 2 to 18 carbon atoms,
C2 to C18 allyloxy group, C2 to C18 alkoxycarbonyl group, C1 to C18 alkylthio group, C1 to C18 alkylsulfonyl group or C1 to C18 alkylsulfinyl group, R ³ represents hydrogen, an aryl group or an alkyl group having 1 to 18 carbon atoms.

The anionic ligands represented by X and X1 in the general formulas (A), (B) and (C) are those having a negative charge when the coordination to the central metal is removed. Group. Such groups include, for example, hydrogen,
Halogen, CF ₃ CO ₂ , CH ₃ CO ₂ , CFH ₂ CO ₂ ,
(CH ₃ ) ₃ CO, (CF ₃ ) ₂ (CH ₃ ) CO, (CF ₃ )
(CH ₃ ) ₂ CO, alkyl group having 1 to 5 carbon atoms, 1 carbon atom
To 5, an alkoxy group, a phenyl group, a phenoxy group, a tosyl group, a mesyl group, and a trifluoromethanesulfonate group.
Chlorine). Further, the neutral electron donating group in L and L1 in the general formulas (A) and (B) is a group having a neutral charge when the coordination to the central metal is removed.
Examples of such a group include PR ² R ³ R ⁴ (where R ² is a secondary alkyl group or a cycloalkyl group, R ³
And R ⁴ are each independently an aryl group, having 1 to 1 carbon atoms.
0 represents a primary alkyl group, a secondary alkyl group, or a cycloalkyl group. ), Pyridine, p-fluoropyridine, etc., and particularly preferred are both -P (cyclohexyl) ₃ ,-
P (cyclopentyl) ₃ or -P (isopropyl) ₃ .

The above metal carbene compound can be obtained by a known synthesis method. For example, Organometallics
Vol. 16, No. 18, p. 3867 (1997) using propargyl chloride. An example of the synthesis of the catalyst is shown below. (Synthesis example) 500 ml Fisher-Porter
A bottle is charged with cyclooctadiene ruthenium dichloride (21 mmol), tricyclohexylphosphine (42 mmol), sodium hydroxide (7.2 g), and 250 ml of sec-butanol from which oxygen has been removed, and heated at 90 ° C. under 2 atmospheres of hydrogen. Pressurization is repeated several times until the absorption of hydrogen is completed, and stirring is continued overnight. Cool to room temperature while applying hydrogen pressure to obtain a pale yellow precipitate. 30 ml of water was added and the precipitate was filtered and dried in a stream of hydrogen to obtain Ru (H) ₂ (H ₂ ) ₂ (Pcy ₃ ) ₂ (yield about 80%) (Pcy ₃ is phosphorus With atoms, and 3
Cyclohexyl groups represented by cy are bonded). next,
This Ru (H) ₂ (H ₂ ) ₂ (Pcy ₃ ) ₂ (1.5 mm
l) was dissolved in 30 ml of dichloroethane solution,
Cool. Add 3-chloro-3-methyl-1-butyne (1.5 mmol). The solution immediately turns reddish purple and is allowed to react for 15 minutes. The cooling bath was removed and degassed methanol (20 ml) was added to precipitate purple crystals. After washing with methanol and drying, the Ru carbene catalyst (Cl) ₂ (Pcy ₃ ) ₂ Ru of the general formula (B) is used.
= CH-CH = obtain a _{C (CH 3) 2 (95} % yield).
(Reference: Organometallics Vol. 16, No. 18, p. 3867 (1997))

The metathesis catalysts include those described above. The addition amount of the catalyst is 0.001 to 5 parts by weight based on 100 parts by weight of the total amount of cycloolefin monomers. 0.01 to 1 part by weight. Also, because of its good stability in air as a catalyst,
One-component metal carbene type catalysts are preferred.

A thermoplastic resin can be added to the cycloolefin composition of the present invention, if necessary, for the purpose of improving adhesion and reducing shrinkage. The thermoplastic resin is not particularly limited, and examples of the thermoplastic resin include olefin-based resins and modified products thereof (modified olefin-based resins), styrene-based resins and modified products thereof (modified styrene-based resins), ionomer resins, and polyolefin resins. Examples include methyl methacrylate, polybutadiene, polyisoprene, polyurethane, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, fluororesin, polyamide, saturated polyester, and petroleum resin.

Various additives such as a thixotropic agent, a colorant, an antifoaming agent, a dispersant, an antioxidant, and a plasticizer are added to the cycloolefin composition of the present invention for the purpose of improving physical properties, appearance and molding workability. Can be contained.

Examples of the thixotropic agent include silica, asbestos powder,
Inorganic thixotropic agents such as fatty acid-treated calcium carbonate, organic bentonite, modified polyester polyol type organic thixotropic agents,
Examples include colloidal silica, fatty acid amide wax, and stearic acid amide.

As a coloring agent, inorganic pigments such as titanium oxide, cobalt blue, cadmium yellow, molybdenum red, chromium oxide, and alumina white, and organic pigments such as carbon black, aniline black, phthalocyanine, and quinacdrine can also be added.

As the defoaming agent, in addition to silicone oils and surfactants, those commercially available from BYK Chemie and Kusumoto Kasei Co., Ltd. can be used.

The cycloolefin composition containing the filler of the present invention can be easily obtained by uniformly mixing the above components at room temperature or under heating. If necessary, defoaming may be performed under reduced pressure.

When the cycloolefin composition containing the filler of the present invention is molded, it is usually molded by a known molding method such as casting, injection molding, hollow molding, extrusion molding, compression molding, and rotational molding. At this time, heating may be performed if necessary.

[0051]

The present invention will be specifically described below with reference to examples. In the examples, “parts” means “parts by weight” unless otherwise specified. Dicyclopentadiene is abbreviated as DCPD.
The metathesis polymerization catalyst used is shown below. This is the catalyst synthesized in the above synthesis example.

[0052]

Embedded image

Each compound obtained in each of Examples and Comparative Examples was prepared as a test piece by the following method and evaluated.

(1) Bending characteristics (a) Method of preparing test piece 0.10 parts of the catalyst was added to the compound and mixed, and then the compound was defoamed under reduced pressure. Thick this compound 3
The mold was cast in a mold capable of forming a flat plate having a thickness of 2 mm, and then the mold was heated in an oven at 40 ° C. for 5 hours and at 130 ° C. for 2 hours to obtain a flat cured product. (B) Bending test A bending test piece having a width of 25 mm and a length of 80 mm was cut out from a flat plate and subjected to a bending test (test speed 2) according to JIS K7203.
mm / min). At this time, the bending deflection rate was determined by the following equation. Deflection rate (%) = 6 dv / l ² d: Deflection amount at break (mm) v: Thickness of test piece (mm) l: Distance between fulcrums (mm)

(2) Water Resistance The retention was determined from the strength of dielectric breakdown before and after the pressure cooker test (PCT) test. (A) Test piece preparation method 0.10 parts of the catalyst was added to the compound and mixed, and then the compound was defoamed under reduced pressure. This compound has a thickness of 2
The mold was cast in a mold capable of forming a flat plate having a thickness of 2 mm, and then the mold was heated in an oven at 40 ° C. for 5 hours and at 130 ° C. for 2 hours to obtain a flat cured product. (B) Insulation breakdown strength This was performed according to JIS K6911. (C) PCT conditions Temperature: 121 ° C Pressure: 2.2 atm Time: 50 hours

(3) Viscosity The viscosity of the compound was evaluated using a BL type viscometer. Temperature: 30 ° C. Number of rotations: 60 rpm Rotor: No. 3

Example 1 DCPD having a purity of about 98% by weight
2 parts of Sumilizer BHT (trade name, manufactured by Sumitomo Chemical Co., Ltd., antioxidant) and 100 parts of triphenylphosphine (trade name, manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) 0.0
Five parts and 2.0 parts of AZ-6171 (trade name, n-hexyltriethoxysilane, manufactured by Nippon Unicar Co., Ltd.) were added and dispersed to prepare a DCPD resin solution. Thereafter, 150 parts of fused silica (average particle size of about 5 μm) was added and mixed to obtain a compound. This compound was heated at 60 ° C. for 4 hours, and then cooled to about 35 ° C. before use.

Example 2 DCPD having a purity of about 98% by weight
2 parts of Sumilizer BHT (trade name, manufactured by Sumitomo Chemical Co., Ltd., antioxidant), 0.05 parts of triphenylphosphine (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) in 100 parts,
A-137 (trade name, manufactured by Nippon Unicar Co., Ltd., n-octyltriethoxysilane) (2.0 parts) was added and dispersed, and D was added.
A CPD resin solution was prepared. Thereafter, 150 parts of fused silica (average particle size of about 5 μm) was added and mixed to obtain a compound. This compound was heated at 60 ° C. for 4 hours, and then cooled to about 35 ° C. before use.

Example 3 DCPD having a purity of about 98% by weight
2 parts of Sumilizer BHT (trade name, manufactured by Sumitomo Chemical Co., Ltd., antioxidant) and 100 parts of triphenylphosphine (trade name, manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) 0.0
5 parts, SID2265.0 (trade name, manufactured by Chisso Corporation,
Reagent, n-decyltriethoxysilane) 2.0 parts,
This was dispersed to prepare a DCPD resin solution. Thereafter, 150 parts of fused silica (average particle size of about 5 μm) was added and mixed to obtain a compound. This compound was heated at 60 ° C. for 4 hours, and then cooled to about 35 ° C. before use.

Example 4 DCPD having a purity of about 98% by weight
100 parts of Sumilyzer BHT (Sumitomo Chemical Co., Ltd., antioxidant) 2 parts, triphenylphosphine (Wako Pure Chemical Industries, Ltd., reagent grade) 0.05
And 2.0 parts of SIO6645.0 (trade name, reagent, n-octadecyltriethoxysilane manufactured by Chisso Corporation) were added and dispersed to prepare a DCPD resin solution. Thereafter, 150 parts of fused silica (average particle size of about 5 μm) was added and mixed to obtain a compound. This compound was heated at 60 ° C. for 4 hours, and then cooled to about 35 ° C. before use.

Example 5 DCPD having a purity of about 98% by weight
2 parts of Sumilizer BHT (trade name, manufactured by Sumitomo Chemical Co., Ltd., antioxidant) and 100 parts of triphenylphosphine (trade name, manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) 0.0
5 parts, SIO6645.0 (trade name, manufactured by Chisso Corporation,
2.0 parts of a reagent, n-octadecyltriethoxysilane) and 0.15 parts of Prenact KR-55 (trade name, manufactured by Ajinomoto Fine Techno Co., Ltd., titanium-based coupling agent) were added and dispersed to prepare a DCPD resin solution. . Thereafter, 150 parts of fused silica (average particle size of about 5 μm) was added and mixed,
I got the compound. This compound was heated at 60 ° C. for 4 hours, and then cooled to about 35 ° C. before use.

(Example 6) DCPD having a purity of about 98% by weight
2 parts of Sumilizer BHT (trade name, manufactured by Sumitomo Chemical Co., Ltd., antioxidant) and 100 parts of triphenylphosphine (trade name, manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) 0.0
5 parts, SIO6627.0 (trade name, manufactured by Chisso Corporation,
Reagent, n-octadecylmethyldiethoxysilane) 2.0
And dispersed to prepare a DCPD resin solution. Thereafter, 150 parts of fused silica (average particle size of about 5 μm) was added and mixed to obtain a compound. This compound was heated at 60 ° C. for 4 hours, and then cooled to about 35 ° C. before use.

Comparative Example 1 DCPD having a purity of about 98% by weight
In 100 parts, 2 parts of Sumilizer BHT (trade name, manufactured by Sumitomo Chemical Co., Ltd., antioxidant), and triphenylphosphine (trade name, manufactured by Wako Pure Chemical Industries, Ltd., special grade of reagent) 0.0
6 parts were added and dispersed to prepare a DCPD resin solution. Thereafter, 150 parts of fused silica (average diameter: about 5 μm) was added and mixed to obtain a compound. This compound was heated at 60 ° C. for 4 hours, and then cooled to about 35 ° C. before use.

Comparative Example 2 DCPD having a purity of about 98% by weight
In 100 parts, 2 parts of Sumilizer BHT (trade name, manufactured by Sumitomo Chemical Co., Ltd., antioxidant), and triphenylphosphine (trade name, manufactured by Wako Pure Chemical Industries, Ltd., special grade of reagent) 0.0
6 parts and 2.0 parts of A-171 (trade name, vinyltrimethoxysilane, manufactured by Nippon Unicar Co., Ltd.)
A CPD resin solution was prepared. Thereafter, 150 parts of fused silica (average particle size of about 5 μm) was added and mixed to obtain a compound. This compound was heated at 60 ° C. for 4 hours, and then cooled to about 35 ° C. before use.

Comparative Example 3 DCPD having a purity of about 98% by weight
In 100 parts, 2 parts of Sumilizer BHT (trade name, manufactured by Sumitomo Chemical Co., Ltd., antioxidant), and triphenylphosphine (trade name, manufactured by Wako Pure Chemical Industries, Ltd., special grade of reagent) 0.0
6 parts and 2.0 parts of a silane coupling agent A-187 (trade name, manufactured by Nippon Unicar Co., Ltd., γ-glycidoxypropyltrimethoxysilane) were added and dispersed to prepare a DCPD resin solution. Then, fused silica (average particle size about 5 μm)
150 parts were added and mixed to obtain a compound. This compound was heated at 60 ° C. for 4 hours, and then cooled to about 35 ° C. before use.

Comparative Example 4 DCPD having a purity of about 98% by weight
In 100 parts, 2 parts of Sumilizer BHT (trade name, manufactured by Sumitomo Chemical Co., Ltd., antioxidant), and triphenylphosphine (trade name, manufactured by Wako Pure Chemical Industries, Ltd., special grade of reagent) 0.0
6 parts and 2.0 parts of A-163 (trade name, methyltrimethoxysilane, manufactured by Nippon Unicar Co., Ltd.)
A CPD resin solution was prepared. Thereafter, 150 parts of fused silica (average particle size of about 5 μm) was added and mixed to obtain a compound. This compound was heated at 60 ° C. for 4 hours, and then cooled to about 35 ° C. before use.

Comparative Example 5 DCPD having a purity of about 98% by weight
In 100 parts, 2 parts of Sumilizer BHT (trade name, manufactured by Sumitomo Chemical Co., Ltd., antioxidant), and triphenylphosphine (trade name, manufactured by Wako Pure Chemical Industries, Ltd., special grade of reagent) 0.0
6 parts, SIP6918.0 (trade name, manufactured by Chisso Corporation,
2.0 parts of a reagent, n-propyltrimethoxylane) was added and dispersed to prepare a DCPD resin solution. Thereafter, 150 parts of fused silica (average particle size of about 5 μm) was added and mixed to obtain a compound. This compound was heated at 60 ° C. for 4 hours, and then cooled to about 35 ° C. before use.

(Comparative Example 6) DCPD having a purity of about 98% by weight
In 100 parts, 2 parts of Sumilizer BHT (trade name, manufactured by Sumitomo Chemical Co., Ltd., antioxidant), and triphenylphosphine (trade name, manufactured by Wako Pure Chemical Industries, Ltd., special grade of reagent) 0.0
6 parts and 2.0 parts of LS-4230 (trade name, reagent, n-pentyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) were added and dispersed to prepare a DCPD resin solution. afterwards,
150 parts of fused silica (average particle size of about 5 μm) was added and mixed to obtain a compound. This compound was heated at 60 ° C. for 4 hours, and then cooled to about 35 ° C. before use.

Table 1 shows the evaluation results. It can be seen that the examples using alkylsilanes having 6 or more carbon atoms have a larger deflection rate and a higher toughness than the comparative examples. Further, it can be seen that in each of the examples, there is no decrease in the dielectric breakdown strength after PCT, and the examples are excellent in water resistance. Further, those using a titanium-based coupling agent in combination have further excellent mechanical properties and can significantly reduce the viscosity.

[0070]

[Table 1]

Next, DCPD was added to the cycloolefin monomer.
And examples using cyclooctadiene. The test method is described below.

(1) Bending characteristics (a) Method for preparing test piece 0.20 parts of catalyst was added to the compound, mixed, and then the compound was degassed under reduced pressure. Thick this compound 3
mm in a mold that can form a flat plate, and then heat the mold in an oven at 25 ° C for 2 hours, then to 100 ° C over 3 hours, and further heat at 100 ° C for 3 hours. A cured product was obtained. (B) Bending test A bending test piece having a width of 25 mm and a length of 80 mm was cut out from a flat plate and subjected to a bending test (test speed: according to JIS K7203).
(500 mm / min). At this time, the bending deflection rate was determined by the following equation. Deflection rate (%) = 6 dv / l ² d: Deflection amount at break (mm) v: Thickness of test piece (mm) l: Distance between fulcrums (mm)

(2) Water resistance The retention was determined from the strength of dielectric breakdown before and after the pressure cooker test (PCT) test. (A) Test piece preparation method 0.10 parts of the catalyst was added to the compound and mixed, and then the compound was defoamed under reduced pressure. This compound has a thickness of 2
mm in a mold that can form a flat plate, and then heat the mold in an oven at 25 ° C for 2 hours, then to 100 ° C over 3 hours, and further heat at 100 ° C for 3 hours. A cured product was obtained. (B) Strength of dielectric breakdown JIS K69
Performed according to 11. (C) PCT conditions Temperature: 121 ° C Pressure: 2.2 atm Time: 50 hours

Example 7 DCPD having a purity of about 98% by weight
50 parts, cyclooctadiene (trade name, manufactured by Tokyo Chemical Industry Co., Ltd., 50 parts), Sumilizer BHT (trade name, manufactured by Sumitomo Chemical Co., Ltd., antioxidant), 2 parts, triphenylphosphine (Wako Pure Chemical Industries, Ltd.) 0.05 parts, SID2265.0 (trade name, reagent, n-decyltriethoxysilane, manufactured by Chisso Corporation)
2.0 parts were added and dispersed to prepare a DCPD resin solution.
Thereafter, 150 parts of fused silica (average particle size of about 5 μm) was added and mixed to obtain a compound. This compound is 6
The mixture was heated at 0 ° C for 4 hours, and then cooled to about 35 ° C before use.

(Comparative Example 7) DCPD having a purity of about 98% by weight
50 parts, cyclooctadiene (trade name, manufactured by Tokyo Chemical Industry Co., Ltd., 50 parts), Sumilizer BHT (trade name, manufactured by Sumitomo Chemical Co., Ltd., antioxidant), 2 parts, triphenylphosphine (Wako Pure Chemical Industries, Ltd.) A DCPD resin solution was prepared by adding and dispersing 0.06 parts of a trade name of a company (special grade of reagent). Then, fused silica (average diameter about 5 μm) 15
0 parts were added and mixed to obtain a compound. This compound was heated at 60 ° C. for 4 hours, and then cooled to about 35 ° C. before use.

Comparative Example 8 DCPD having a purity of about 98% by weight
50 parts, cyclooctadiene (trade name, manufactured by Tokyo Chemical Industry Co., Ltd., 50 parts), Sumilizer BHT (trade name, manufactured by Sumitomo Chemical Co., Ltd., antioxidant), 2 parts, triphenylphosphine (Wako Pure Chemical Industries, Ltd.) 0.06 parts, trade name, reagent grade, LS-4230 (trade name, reagent, pentyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
2.0 parts were added and dispersed to prepare a DCPD resin solution.
Thereafter, 150 parts of fused silica (average particle size of about 5 μm) was added and mixed to obtain a compound. This compound is 6
The mixture was heated at 0 ° C for 4 hours, and then cooled to about 35 ° C before use.

Table 2 shows the evaluation results. It can be seen that the examples using alkylsilanes having 6 or more carbon atoms have a larger deflection rate and a higher toughness than the comparative examples. Further, it can be seen that in each of the examples, there is no decrease in the dielectric breakdown strength after PCT, and the examples are excellent in water resistance.

[0078]

[Table 2]

[0079]

According to the cycloolefin composition of the present invention, it is possible to suppress a decrease in toughness (particularly, a deflection rate in a bending test) without reducing water resistance and electrical insulation. The cycloolefin composition of the present invention and the molded product obtained therefrom have excellent water resistance, boiling resistance, mechanical properties, and electrical properties of the cycloolefin polymer, for example, a septic tank, a bathtub, a kitchen top plate, a tank, It can be used for applications such as unit baths, wall panels, pleasure boats, sewers, water pipes, corrugated sheets, wiring boards, molded products such as insulating materials, electrical components, and electronic components.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Hiromasa Kawai 48 Wadai, Tsukuba, Ibaraki Prefecture Within Hitachi Chemical Co., Ltd. (72) Inventor Robert Suchen Chu 48 Wadai, Tsukuba, Ibaraki Hitachi Chemical Co., Ltd. In the laboratory (72) Inventor Akira Sasaki 48 Wadai, Tsukuba, Ibaraki Pref.Hitachi Chemical Industry Co., Ltd. (72) Inventor Yoshiki Inoue 48 Wadai, Tsukuba Ibaraki Pref. Hitachi Chemical Co., Ltd.F-term (Reference) 4J002 CE001 DE077 DE147 DJ007 DJ017 DL007 EX036 EZ008 FD017 FD158 4J032 CA22 CA23 CA24 CA28 CA35 CA38 CA43 CA45 CB01 CD02 CE16 CE17 CG07

Claims (9)

[Claims] 1. A cycloolefin comprising (a) a metathesis-polymerizable cycloolefin monomer, (b) a filler, (c) an alkylsilane coupling agent represented by the general formula (1), and (d) a metathesis polymerization catalyst. Olefin composition. (R) n -Si- (R ¹ ) 4-n (1) wherein R represents an alkyl group, at least ^one of which is an alkyl group having 6 or more carbon atoms, and R ¹ is Each independently represents an alkoxy group, wherein n is an integer of 1 to 3] 2. (a) 100 parts by weight of a metathesis-polymerizable cycloolefin monomer, (b) 1 to 99% by weight of a filler based on the total amount of the composition, and (c) a compound represented by the general formula (1). The alkylsilane coupling agent to be used is
The cycloolefin composition according to claim 1, wherein 0.01 to 20 parts by weight per 0 parts by weight, and 0.001 to 5 parts by weight of the metathesis polymerization catalyst (d) per 100 parts by weight of the cycloolefin monomer. . 3. The cycloolefin composition according to claim 1, wherein the metathesis polymerization catalyst is a ruthenium compound. 4. The cycloolefin composition according to claim 1, wherein the metathesis polymerization catalyst is a catalyst represented by the general formula (A). Embedded image (M represents ruthenium or osmium, X and X1 each independently represent an anionic ligand, L and L1 each independently represent a neutral electron donating group, and Q and Q1 each independently represent hydrogen, alkyl Group, alkenyl group or aromatic group, and the alkyl group, alkenyl group or aromatic group may have a substituent.) 5. The cycloolefin composition according to claim 1, wherein the metathesis polymerization catalyst is a catalyst represented by the general formula (B). Embedded image (M represents ruthenium or osmium, X and X1 each independently represent an anionic ligand, L and L1 each independently represent a neutral electron donating group, and R ¹ and R ² each independently represent a carbon atom. An alkyl group having 1 to 18 carbon atoms, 2 carbon atoms
Alkenyl group having 2 to 18 carbon atoms, alkynyl group having 2 to 18 carbon atoms, aryl group, carboxylate group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, alkenyloxy group having 2 to 18 carbon atoms, 2 carbon atoms -18 alkynyloxy group, C2-C18 allyloxy group, C2-C1
8 alkoxycarbonyl group, an alkylthio group having 1 to 18 carbon atoms, an alkyl sulfinyl group having an alkylsulfonyl group, or 1 to 18 carbon atoms having 1 to 18 carbon atoms, R ³
Represents hydrogen, an aryl group or an alkyl group having 1 to 18 carbon atoms. ) 6. The cycloolefin composition according to claim 1, wherein the metathesis polymerization catalyst is a catalyst represented by the general formula (C). Embedded image (M represents ruthenium or osmium, X and X1 each independently represent an anionic ligand, L and L1 each independently represent a neutral electron donating group, and Q and Q1 each independently represent hydrogen, alkyl Group, alkenyl group or aromatic group, and the alkyl group, alkenyl group or aromatic group may have a substituent.) 7. The cyclo according to claim 1, wherein (b) one of glass, silica, alumina, magnesium hydroxide, aluminum hydroxide and silica sand is contained as one component of the filler. Olefin composition. 8. The cycloolefin composition according to claim 1, comprising (a) dicyclopentadiene as one of the cycloolefin monomer components. 9. A molded article comprising the cycloolefin composition according to any one of claims 1 to 8.