KR20010110448A - Cycloolefin composition, process for producing the same, molding material, and molded object - Google Patents

Abstract

In the present invention, a cycloolefin composition comprising a metathesis polymerizable cycloolefin monomer, a coupling agent, and a metathesis polymerization catalyst, the composition comprising a metal-containing coupling agent or a reactive polysiloxane as a coupling agent, and the composition The manufacturing method of this, the molding material containing this composition, and the molded object which is its hardened | cured material are provided.

Description

Cycloolefin composition and its manufacturing method, molding material and molded body TECHNICAL FIELD {CYCLOOLEFIN COMPOSITION, PROCESS FOR PRODUCING THE SAME, MOLDING MATERIAL, AND MOLDED OBJECT}

It is conventionally known that cycloolefins ring-opening metathesis polymerization by a metathesis polymerization catalyst system. For example, J. Am. Chem. Soc., 1960, Vol. 82, p. 2337 discloses that ring-opening metathesis polymerization of norbornene with a metathesis catalyst system is described in Angew, Chem. Int. Edn., 1964, Vol. 3, p. 723 discloses the ring-opening metathesis polymerization of cyclopentene by the metathesis catalyst system [MoCl ₅ / Al (C ₂ H ₅ ) ₃ ].

Moreover, the method of ring-opening metathesis polymerization of cycloolefins and manufacturing a polymer is also known. For example, Japanese Patent Application Laid-Open No. 50-130900 or Japanese Patent Application Laid-open No. 52-33000 disclose a method for producing a ring-opening metathesis polymerized polymer using a metathesis catalyst system composed of a halide such as tungsten or molybdenum and an organoaluminum compound. Is disclosed.

On the other hand, a method of bulk polymerizing norbornene-type monomers such as dicyclopentadiene and tricyclopentadiene by reaction injection molding (RIM) is also known to obtain a crosslinked polymer molded product. The reaction injection molding is a molding method in which two kinds of solutions reacting with each other are subjected to collision mixing, the mixed solution is directly injected into the mold as a liquid, and the ring-opening metathesis polymerization is carried out as a mass.

For example, Japanese Patent Application Laid-Open No. 58-127728 or Japanese Patent Laid-Open No. 58-129013 includes Solution A consisting of a mixture of a catalyst component and a monomer of a metathesis catalyst system, and a mixture of an activator and a monomer of the metathesis catalyst system. A method of reaction injection molding solution B to obtain a crosslinked polymer molding is disclosed.

Japanese Unexamined Patent Publication No. 59-51911 uses a metathesis catalyst system combining a catalyst component selected from organic ammonium salts of tungsten and molybdenum and an activator selected from alkoxyalkyl aluminum halides and aryloxyaluminum halides to react norbornene-type monomers. A method of injection molding to produce crosslinked polymer moldings is disclosed.

Further, Japanese Patent Application Laid-Open No. 3-205409 discloses a reaction injection using a metathesis catalyst system combining a catalyst component selected from tungsten hexachloride and tungsten oxytetrachloride and an activator selected from diethylaluminum chloride and ethylaluminum dichloride. A method for producing a dicyclopentadiene polymer crosslinked by a molding method is disclosed.

In these metathesis catalyst systems, the catalyst component is activated by an activator, and it can be seen that the ring-opening metathesis polymerization of the norbornene-type monomer. In the metathesis catalyst system, it is known that a catalyst component is activated by a cocatalyst (activator) component to ring-open metathesis polymerization of norbornene-type cycloolefins.

It is known that the hardened | cured material obtained in this way (namely, the polymer of cycloolefin) is generally excellent in the point of mechanical property, an electrical property, and water resistance. For example, when the bending test is performed, the steel sheet is exhibited, and the deformation rate is also considerably large, and the toughness is higher than that of other thermosetting resins such as epoxy resins and unsaturated polyester resins.

However, when the filler is added to the cycloolefin composition, an increase in the viscosity of the compound is remarkable, and workability deteriorates. For this reason, when using a filler conventionally, it was known that it is preferable to add a coupling agent in order to reduce a viscosity. For example, Japanese Patent Application Laid-Open No. 02-185558 discloses a norbornene-based silane coupling agent, and Japanese Patent Application Laid-open No. 02-276852 discloses an aryl silane coupling agent and a vinyl silane coupling agent. Coupling agent is shown.

However, when the silane coupling agent is used, the elastic modulus of the polymer is increased by the adhesion between the resin and the filler, and further, the bending during the bending test is also reduced, so that the toughness which is one of the characteristics of the cycloolefin composition is lost. there is a problem.

This invention relates to the cycloolefin composition containing cycloolefins, its manufacturing method, the molding material using the said composition, and the molded object obtained by hardening | curing the said molding material.

An object of the present invention is to provide a cycloolefin composition excellent in workability and mechanical properties, a method for producing the composition, a molding material and a molded article even when a filler is used.

In order to achieve this object, the present inventors have studied various coupling agents, and as a result, by using a specific coupling agent, it is possible to make bulk addition of fillers while ensuring the toughness of cycloolefins and workability of the composition. It has been found that the present invention has been achieved. That is, the present invention provides a cycloolefin composition comprising a metathesis polymerizable cycloolefin monomer, a coupling agent, and a metathesis polymerization catalyst, wherein the coupling agent includes a metal-containing coupling agent or a reactive polysiloxane. The cycloolefin composition of the present invention may comprise a filler.

Moreover, in this invention, the manufacturing method of the composition of this invention, the molding material containing this composition, and the molded object which is its hardened | cured material are provided.

The metal-containing coupling agent has a fast reaction with cycloolefins and a filler, and can improve workability as it maintains mechanical properties. The metal-containing coupling agent used in the present invention is different from the conventional silane coupling agents, and is effective in fillers having no hydroxyl group such as calcium carbonate. In addition, there is an advantage that the heat treatment time for reacting the coupling agent and the filler is shortened.

Moreover, since reactive polysiloxane can absorb the nonuniformity of the aspect of resin and a filler, it can make the other characteristics the same as that of the prior art, maintaining the toughness of a polymer. Since the reactive polysiloxane used in the present invention is excellent in adhesiveness, it is preferable because a decrease in water resistance and electrical insulation due to interfacial peeling between the filler and the resin can be avoided.

Best Mode for Carrying Out the Invention

A. Cycloolefin Monomers

The cycloolefin monomers used in the present invention may be any of those useful in metathesis polymerization. Especially, substituted or unsubstituted norbornene-type cycloolefins, such as norbornene, dicyclopentadiene, and dihydrodicyclopentadiene, are used preferably.

As norbornene-type cycloolefins,

Bicyclic norbornenes such as norbornene, methyl norbornene, dimethyl norbornene, ethyl norbornene, ethylidedenyl norbornene, and butyl norbornene,

Tricyclic norbornenes such as dicyclopentadiene (dimer of cyclopentadiene), dihydrodicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene,

Tetracyclic norbornenes such as tetracyclododecene, methyltetracyclododecene, dimethylcyclotetradodecene, and

And five or more rings of norbornene, such as tricyclopentadiene (trimer of cyclopentadiene) and tetracyclopentadiene (tetramer of cyclopentadiene), are mentioned. It is also possible to use cyclobutene, cyclopentene, cyclooctene, cyclooctadiene, cyclooctatriene, cyclododecatene, and the like. Moreover, dicyclopentadiene type petroleum resin etc. which are obtained by heat-polymerizing or cation-polymerizing dicyclopentadiene can also be used. These cycloolefins can be used combining 1 type (s) or 2 or more types.

Moreover, it is also possible to use the compound which has two or more norbornene groups, for example, norbornadiene, tetracyclo dodecadiene, a symmetric tricyclopentadiene, etc. as a polyfunctional crosslinking agent.

Among the cycloolefins mentioned above, dicyclopentadiene, methyltetracyclododecene, ethylidedenyl norbornene, tricyclopentadiene, and tetracyclopentadiene are preferable, and dicyclopentadiene is particularly preferable from the availability and economical efficiency. desirable.

Commercially available dicyclopentadiene includes impurities such as vinylnorbornene, tetrahydroindene, methylvinylnorbornene, methyltetrahydroindene, methyldicyclopentadiene, dimethyldicyclopentadiene, tricyclopentadiene, and the like. As what is contained, the dicyclopentadiene of various purity is marketed. The dicyclopentadiene used in the present invention also varies depending on the intended use of the polymer to be obtained, but usually 80% or more pure, preferably 90% or more pure.

In the use of dicyclopentadiene, a part of dicyclopentadiene is made into cyclopentadiene oligomers, such as tricyclopentadiene and tetracyclopentadiene, by heat-processing beforehand, or vinylnorbornene and methylvinyl novo which are impurities Nene may be isomerized with tetrahydroindene or methyltetrahydroindene. Such prior heat treatment is usually performed at 120 to 250 ° C. for about 0.5 to 10 hours.

Antioxidant can be added to cycloolefins used by this invention as needed. In addition, commercially available dicyclopentadiene contains antioxidants such as approximately 2,6-di (t-butyl) -4-methylphenol and 4-t-butylcatechol. In use, the contained antioxidant may be removed or may be added anew.

The antioxidant to be used is not particularly limited as long as it has an antioxidant ability, and examples thereof include hindered phenol antioxidants. For example, 2,6-di (t-butyl) -4-methylphenol, 2,6-di (t-butyl) -4-ethylphenol, stearyl-β- {3,5-di (t-butyl) -4-hydroxyphenyl} propionate, tetraquis- [methylene-3- {3 ', 5'-di (t-butyl) -4'-hydroxyphenyl} propionate] methane, 2,2' Methylenebis (4-ethyl-6-t-butylphenol), 4,4'-methylenebis {2,6-di (t-butyl) phenol}, 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 etc. are mentioned. It is also possible to use amine-based, sulfur-based, phosphorus-based antioxidants and thermal deterioration inhibitors. These may be used individually by 1 type and may be used in combination of 2 or more type. The addition amount of antioxidant is 10-10,000 ppm normally with respect to cycloolefins. Moreover, you may use together an ultraviolet absorber, a light stabilizer, etc. further.

Moreover, in order to adjust a polymerization reaction, you may add reaction modifiers, such as a triphenyl phosphine, a tricyclohexyl phosphine, a tricyclo pentyl phosphine, a tributyl phosphine, and a triisopropyl phosphine. The appropriate amount of the reaction regulator is usually 0.001 to 10 parts by weight based on 100 parts by weight of the raw material monomer.

B. Filling

Compositions and molding materials of the present invention may comprise a filler. Suitable fillers for the present invention include, for example, oxide, hydroxide, carbonate, sulfate, and silicate fillers. A filler may be used individually by 1 type and may be used in combination of 2 or more type. Moreover, the shape can be made into powder form, fibrous form, plate form, etc., and there is no restriction | limiting in particular.

Examples of the oxide-based fillers include silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrites.

Examples of the hydroxide filler include calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, and the like.

Examples of the carbonate filler include calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite and the like.

Examples of the sulfate filler include calcium sulfate, barium sulfate, gypsum fibers and the like.

As silicate-based fillers, calcium silicate (wollastonite, zonothorite), talc, clay, kaolin, mica, montmorillonite, bentonite, activated clay, seviolite, imogolite, sericite, glass powder, glass Fibers, glass beads, glass ballons, shirasu balloons, and the like.

Examples of the nitride-based filler include aluminum nitride, boron nitride, silicon nitride, and the like.

Examples of the carbon-based filler include carbon black, graphite, carbon fiber, carbon balun, charcoal powder, expanded graphite, and the like.

Other fillers include various metal powders, metal fibers, whiskers such as potassium titanate, powders of thermoreversible resins and thermosetting resins, and natural products such as silica sand, crushed stone, gravel, and the like.

Of these fillers, glass, silica, alumina, magnesium hydroxide, aluminum hydroxide and silica sand are particularly preferred.

The addition amount of the filler is 1 to 99% by weight, preferably 5 to 95% by weight, more preferably 30 to 90% by weight based on the total amount of the composition.

C. Coupling Agent

Compositions and molding materials of the present invention include at least any of metal-containing coupling agents and reactive polysiloxanes as coupling agents. These may use either one and may use both together.

As for the usage-amount of the coupling agent used for this invention, 0.05-20 weight part is preferable with respect to 100 weight part of fillers, and 0.1-5 weight part is more preferable. The reason for this is that if the amount used is less than this ratio, the wettability between the filler and the resin becomes insufficient, and improvement effects such as mechanical properties of the composite material are not sufficiently obtained. Moreover, even if it uses more than this ratio, it does not improve a mechanical characteristic and water resistance further, and it is unpreferable from an economic viewpoint.

The coupling agent may be used for pretreatment of the filler, or may be added and used at the time of mixing the resin material and the filler.

When the filler is to be treated in advance, it can be carried out in the same manner as the conventional treatment with the silane coupling agent. For example, in the case of a powdery inorganic filler, the coupling agent may be added directly or diluted in a solvent, mixed with a stirrer such as a Henschel mixer or a super mixer, and then heated to react the coupling agent with the inorganic filler. It is preferable to perform heat processing for 0.5 to 6 hours at room temperature-140 degreeC. In the case of fibrous fillers, the fibers may be immersed in a solution in which the coupling agent is diluted, and then treated under the same heating conditions.

In addition, when adding a coupling agent at the time of mixing a resin material and a filler, for example, after disperse | distributing a coupling agent in a resin material or a filler, the resin material and a filler are mixed, and the filler mentioned above as needed after that. The same heat treatment as in the case of pretreatment of

(a) metal-containing coupling agents

The metal-containing coupling agent used in the present invention is a compound containing a metal atom in a molecule, and in a complex system of an inorganic material and an organic material or a complex system of heterogeneous organic materials, chemically combines or chemically It is a material that improves affinity with reactivity.

As such a metal-containing coupling agent, what the hydrolyzable group couple | bonded with the metal is generally used. Titanium, aluminum, zirconium, iron, calcium, magnesium, zinc, etc. are mentioned as a metal contained in a metal containing coupling agent, Especially titanium, aluminum, zirconium is preferable. The hydrolyzable group is not particularly limited but is preferably an alkoxyl group.

As a titanium coupling agent suitable for this invention, isopropyl triisostearoyl titanate, isopropyl tri-n-dodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, and tetraisopropyl bis ( Dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diaryloxymethyl-1-butyl) bis (ditridecylphosphite) titanate, bis (di Octyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryloyl isostearoyl titanate, isopropyl isostearoyldiate Acryl titanate, isopropyl tri (dioctylphosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N-aminoethyl-aminoethyl) thi Nitrate, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetraquis (2-ethylhexyl) titanate, tetrastearyl titanate, tetramethyl titanate, diethoxybis (acetylacetonate) titanium , Diisopropylbis (acetylacetonate) titanium, diisopropoxybis (ethylacetoacetate) titanium, isopropoxy (2-ethyl-1,3-hexanediolite) titanium, di (2-ethylhexoxyquise) Bis (2-ethyl-1,3-hexanediolite) titanium, di (n-butoxy) bis (triethanol aluminate) titanium, tetraacetylacetonate titanium, hydroxybis (lactat) titanium and the like. .

Moreover, acetoalkoxy aluminum diisopropylate etc. are mentioned as an aluminum type metal containing coupling agent suitable for this invention, and zirconium acetylacetonate bisethyl acetonate etc. are mentioned as a zirconium system.

These may be used individually by 1 type and may use two or more types together.

Of these metal-containing coupling agents, tetra (2,2-diaryloxymethyl-1-butyl) bis {di (tridecyl)} phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, isopropyltristea Loyl titanate and acetoalkoxyaluminum diisopropylate are particularly preferred. This is because they do not have an amino group or the like which inhibits the curing of metathesis polymerization, and thus have a high coupling effect.

In addition to the metal-containing coupling agent described above, other coupling agents such as a silane coupling agent may be used in combination. In particular, when a titanium compound is used as the metal-containing coupling agent, the titanium compound also acts as a catalyst for silanol condensation reaction of the silane coupling agent, so the combination with the silane coupling agent is suitable for the present invention.

As a silane coupling agent which can be used together, a vinylsilane compound (vinyl trimethoxysilane, vinyl triethoxysilane, etc.), an epoxy silane compound ((beta)-(3, 4- epoxycyclohexyl) ethyltrimethoxysilane, (gamma)) -Glycidoxypropyltrimethoxysilane, etc.), aminosilane compounds (γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, etc.), methacryloylsilane compounds ( known silane coupling agents such as γ-methacryloxypropyltrimethoxysilane, or alkylsilane compounds (methyltrimethoxysilane, methyltriethoxysilane, etc.), dimethoxydimethylsilane, diethoxydimethylsilane, and tetramethoxy Alkoxysilanes, such as a silane and tetraethoxysilane, etc. can be used.

(b) reactive polysiloxanes

The reactive polysiloxane used in the present invention is not particularly limited as long as it is a polysiloxane having a hydrolyzable group bonded to a silicon atom. Examples of the hydrolyzable group include a hydrogen atom, an alkoxyl group, an acyloxy group, a methoxymate group, an amino group, an aminooxy group, a mercapto group, an alkenyloxy group and the like, but an alkoxyl group is preferable.

As a reactive polysiloxane suitable for this invention, the compound represented by either of following General formula (1)-(3) is mentioned.

Here, each R is selected independently from each other and represents a hydrogen atom, a monovalent hydrocarbon group or a halogenated alkyl group. R in one molecule may be all the same, and some or all may differ. Examples of the monovalent hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group, phenyl group and phenethyl group. In addition, examples of the halogenated alkyl group include trifluoropropyl group and chloropropyl group. R is particularly preferably a monovalent hydrocarbon group or a halogenated alkyl group, and particularly preferably a methyl group and a fluoroalkyl group.

Y represents the organic reactive functional group represented by following General formula (4).

-R ¹ -X... (4)

R ¹ represents a direct bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and X represents a functional group having organic reactivity. In addition, R ¹ as for example _{-CH 2 -, -CH 2 CH 2} -, -CH 2 CH 2 CH 2 -, -CH (CH 3) CH 2 -, - (CH 2) 4 -, - (CH 2) ₆ -,-(CH ₂ ) _8- , -CH ₂ CH ₂ C ₆ H ₄ -,-(CH ₂ ) ₁₂ -,-(CH ₂ ) ₁₆ and the like, and preferably a propylene group. As X, for example, an epoxy group, an amino group, a hydroxyl group, a carboxyl group, an acyl group, a mercapto group, a methacrylo group, an isocyanate group, a ureide group, a vinyl group, an amide group, an imide group, an imino group, an aldehyde group, a nitro group, Nitrile group, oxime group, azo group, hydrazone group and the like. Specific examples of Y include-(CH ₂ ) ₃ OH,-(CH ₂ ) ₃ SH,-(CH ₂ ) ₃ NH ₂ ,-(CH ₂ ) ₇ COOH, and the like, but are not limited thereto.

Z represents a hydrolyzable group or a condensable silylalkyl group represented by the following general formula (5).

Here, R ² represents an alkylene group having 2 to 5 carbon atoms, R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms selected independently of each other, and r is 2 or 3, but is reactive 2 is preferable at the point.

R ² is an alkylene group having 2 to 5 carbon atoms, such as -CH ₂ CH _2- , -CH ₂ CH ₂ CH _2- , -CH (CH ₃ ) CH ₂ -,-(CH ₂ ) ₄ -,-(CH ₂ ) _{5 and the like} , preferably an ethylene group. R <^3> and R <^4> is a hydrogen atom or C1-C5 alkyl group chosen independently from each other, and a methyl group, an ethyl group, a propyl group, and a butyl group are mentioned, for example. R ³ is preferably a methyl group, and R ⁴ is preferably a methyl group or an ethyl group. Specific examples of the Z group include -CH ₂ CH ₂ Si (OCH ₃ ) ₃ , -CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ , -CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , -CH ₂ CH ₂ Si [OCH (CH ₃ ) ₂ ] ₃ ,-(CH ₂ ) ₃ Si (CH ₃ ) (OC ₂ H ₅ ) ₂ ,-(CH ₂ ) ₅ Si (C ₂ H ₅ ) (OC ₂ H _{5 2} ) etc., but it is not limited to these.

Q represents a polyoxyalkylene group represented by the following general formula (6).

-(CH ₂ ) _p -O- (C ₂ H ₄ O) _m- (C ₃ H ₆ O) _n -R ₅ . (6)

Here, R <^5> represents a hydrogen atom, an acyl group, or monovalent hydrocarbon group, p is 0 or a positive integer, m and n are a positive integer of 0 or 150 or less, but 2 is preferable. M + n is an integer of 1 to 150. As an acyl group applicable as R <^5> , an acetyl group or a propionyl group is mentioned, for example. Moreover, as a monovalent hydrocarbon group, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, or a vinyl group is mentioned, for example.

M ¹ independently of one another represents a group selected from said R, Y, Z and Q. M ² independently represents a group selected from R, Y and Z. M ³ independently of one another represents a group selected from said R and Y. Two M ^{1 to} M ³ in one molecule may be the same or different from each other.

a is an integer of 0-500, b is an integer of 0-200, d is an integer of 0-200, and e is an integer of 0-200. However, when b is 0, M ¹ is Y, and both d and e are integers of 1 or more. When d is 0, M ¹ is Z, and both b and e are integers of 1 or more. When e is 0, M ¹ is Q, and both b and d are integers of 1 or more.

f is an integer of 0-500, g is an integer of 0-200, h is an integer of 0-200. However, when g is 0, M <^2> is Y and h is an integer of 1 or more. When h is 0, M <^2> is Z and f is an integer of 1 or more.

j is an integer of 0-500, k is an integer of 0-500. However, when k is 0, M ³ is Z.

As the compound of the general formula (1), for example, a compound in which Y is an epoxy group, Z is a condensable silylalkyl group having an alkoxyl group bonded to silicon, and Q is a polyether group, is sold as MAC-2101 from Japan Uniker Co., Ltd. .

D. Metathesis Polymerization Catalyst

The metathesis polymerization catalyst used in the present invention is applicable as the catalyst system for the ring-opening metathesis polymerization of the cycloolefin-based compound, and examples thereof include a two-component catalyst and a one-component catalyst. none. However, from the improvement of stability in air, a one-component metal carbene type catalyst is preferable.

The addition amount of a metathesis catalyst is 0.001-5 weight part with respect to a total of 100 weight part of cycloolefin monomers normally, It is preferable to set it as 0.01-1 weight part from an economic point.

The two-component metathesis polymerization catalyst is a catalyst system combining a catalyst component and an activator. The two-component metathesis polymerization catalyst used in the present invention includes transition metals such as titanium, vanadium, molybdenum, tungsten, rhenium, iridium, ruthenium and osmium, and complex metal halides, metal carbenes or Ziegler-Na (Ziegler- Natta) type coordination catalyst.

Specifically, tungsten compounds such as tungsten hexachloride, tungsten oxy tetrachloride, tungsten oxide, and tridecyl ammonium tungsten, molybdenum chloride, molybdenum oxychloride, molybdenum oxide, and molybdenum compounds such as tridecyl ammonium molybdenum, and tantalum compounds such as tungsten chloride And [(cyclohexyl) ₃ P] ₂ RuCl ₂ , [(phenyl) ₃ P] ₃ RuCl ₂ , (cyclohexyl) ₃ P (p-cymene) RuCl ₂ , [(phenyl) ₃ P] ₃ (CO) RuH Ruthenium compounds, such as _2, etc. are mentioned.

A well-known cocatalyst (activator) is used together in these two-component metathesis polymerization catalyst systems as needed. Specific examples thereof include an alkyl aluminum halide, an alkoxy alkyl aluminum halide, an aryloxy alkyl aluminum halide, an organotin compound, and the like.

A one-component metathesis polymerization catalyst is different from a two-component catalyst system, and does not easily lose catalytic activity due to moisture in the air or adsorbed water on a solid surface. Can be polymerized. As such a one-component metathesis polymerization catalyst, specifically, a metal carbene type stabilized against moisture by having a structure in which a ligand having a high steric hindrance is coordinated with a center metal by a metal carbene structure of ruthenium or osmium as a central skeleton A coordination catalyst.

Preferred examples of these ruthenium or osmium metal carbene coordination catalysts include compounds represented by any of the following general formulas (7) to (9). Among them, the compound represented by the general formula (9) is particularly preferable in terms of the degree of catalytic activity, the degree of synthesis yield, and economic efficiency.

Here, M represents ruthenium or osmium.

X ¹ and X ² each represent an anionic ligand selected independently. Anionic ligands are those atoms or groups of atoms having a negative charge when the coordination to the central metal is removed. Examples of this anionic ligand include 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} there is a CO, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, a phenyl group, a phenoxy group, a tosyl group, mesyl group, methane sulfonate group trifluoromethyl. It is particularly preferred that X ¹ and X ² are both halogen (particularly chlorine).

L ¹ and L ² each represent a neutral ligand selected independently. The neutral ligand is an atom or group of atoms having a neutral charge when the coordination to the central metal is removed. Such groups include, for example, PR ⁸ R ⁹ R ¹⁰ (wherein R ⁸ is a secondary alkyl group or a cycloalkyl group, R ⁹ and R ¹⁰ are aryl groups, primary alkyl groups and secondary alkyl groups having 1 to 10 carbon atoms, and Phosphine-based electron donors represented by the group independently selected from cycloalkyl groups). It is particularly preferable that both L ¹ and L ² are P (cyclohexyl) ₃ , P (cyclopentyl) ₃ , or P (isopropyl) ₃ .

Examples of the ligand include pyridine, p-fluoropyridine, imidazolidene and the like. As an imidazolidene compound, the heterocyclic compound represented by following General formula (10) or (11) is preferable. Among these, it is particularly preferable to use the compound represented by the formula (11) as a ligand.

Herein, R ¹¹ and R ¹² are each selected independently and are an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group, and an aryl group. Moreover, R <^11> and R <^12> may be substituted by the C1-C10 alkyl group, the C1-C10 alkoxyl group, and the aryl group, Moreover, these groups are halogen, the C1-C5 alkyl group, C1-C5 It may be substituted by the alkoxyl group and the phenyl group. In terms of thermal stability, at least one of R ¹¹ and R ¹² is preferably a group represented by the following general formula (12).

In this formula (12), R <^13> and R <^14> is hydrogen, a C1-C3 alkyl group, or a C1-C3 alkoxyl group, respectively, R <^15> hydrogen, a C1-C10 alkyl group, an aryl group , Hydroxyl group, thiol group, thioether group, ketone group, aldehyde group, ester group, ether group, amine group, imine group, amide group, nitro group, carboxylic acid group, disulfide group, carbonate group, isocyanate group, Carbodiimide groups, carboalkoxy groups, carbamate groups, halogens and the like.

Specific examples of the imidazolidene compound that can be used as the ligand include carbene represented by the following structural formula (13) or structural formula (14). Among these, the imidazolidene compound of Structural Formula (13) is particularly preferable in terms of polymerization activity.

Specific examples of the catalyst suitable for the present invention include the following structural formulas (15) to (17).

Q ¹ and Q ² each independently represent a hydrogen, alkyl group, alkenyl group or aromatic group, and the alkyl group, alkenyl group or aromatic group may have a substituent.

R ⁵ and R ⁶ are each independently selected an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group, a carboxylate group having 1 to 18 carbon atoms, and 1 to C carbon atoms. An alkoxyl group having 18, an alkenyloxy group having 2 to 18 carbon atoms, an alkynyloxy group having 2 to 18 carbon atoms, an aryloxy group having 2 to 18 carbon atoms, an alkoxycarbonyl group having 2 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, and carbon atoms An alkylsulfonyl group having 1 to 18 or an alkylsulfinyl group having 1 to 18 carbon atoms is represented, and R ⁷ represents hydrogen, an aryl group or an alkyl group having 1 to 18 carbon atoms.

Such a metal carbene compound can be obtained by a known synthesis method. For example, the method using the propargyl chloride shown in Organometallics Vol. 16, 18, p. 3867 (1997) is mentioned. The synthesis example of a catalyst is shown below (Ref .: Organometallics No. 16, 18, p. 3867 (1997)). Cy represents a cyclohexyl group.

Synthesis Example

In a 500 ml Fisher-Porter bottle, cyclooctadiene ruthenium dichloride (21 mmol), tricyclohexylphosphine (42 mmol), sodium hydroxide (7.2 g) and 250 ml of deoxygenated sec-butanol were placed in a 90-mL hydrogen atmosphere at 200 kPa. Heat at 캜. Pressurization is repeated several times until absorption of hydrogen is complete, and stirring is continued overnight. It cools to room temperature under pressure of hydrogen, and obtains a pale yellow precipitate. 30 ml of water is added, and the precipitate is filtered and dried in a hydrogen stream to obtain Ru (H) ₂ (H ₂ ) ₂ (P (cy) ₃ ) ₂ (yield about 80%). Next, this Ru (H ₂ ) (H ₂ ) ₂ (P (cy) ₃ ) ₂ (1.5 mmol) is dissolved in 300 ml of dichloroethane and cooled to -30 ° C. 3-Chloro-3-methyl-1-butyl (1.5 mmol) is added. The solution turns red purple immediately, reacts for 15 minutes as it is, and then the cooling bath is removed and degassed methanol (20 ml) is added to precipitate purple crystals. Washed with methanol and dried to give Ru carbene catalyst (Cl) ₂ (P (cy) ₃ ) ₂ Ru = CH-CH = C (CH ₃ ) ₂ (yield 95%).

E. Thermoplastic

A thermoplastic resin can be added to the cycloolefin composition and the molding material of the present invention as necessary, for example, for adhesion improvement or low shrinkage.

The applicable thermoplastic resin is not particularly limited, but for example, an olefin resin and its modified body (modified olefin resin), styrene resin and its modified body (modified styrene resin), ionomer resin, polymethyl methacrylate, poly Butadiene, polyisoprene, polyurethane, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, fluorine resin, polyamide, saturated polyester, petroleum resin and the like.

F. Additive

The cycloolefin composition and the molding material of the present invention may contain various additives such as thixotropic agents, colorants, antifoaming agents, dispersants, antioxidants, reversible agents, etc. for the purpose of improving physical properties, appearance, molding workability, and the like.

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

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

As the antifoaming agent, other commercial products such as silicone oils and surfactants (for example, commercially available from Byk Kemina Kusumoto Kasei, etc.) can be used.

G. Manufacturing Method and Forming Method

The cycloolefin composition and the molding material of the present invention can be obtained by uniformly mixing the above-mentioned components under normal temperature or heating. Moreover, you may perform defoaming by pressure reduction as needed.

The cycloolefin composition or molding material of the present invention, molding, injection molding, blow molding, extrusion molding, compression molding, rotational molding and the like can be applied to any shape by applying a known molding method. In shaping | molding, you may heat as needed.

The molded article of the present invention is a building material such as a water purification tank, a bath tub, a kitchen top plate, a water purification tank, a wall panel, a sewage tank, a drainage pipe, a wave plate, in addition to electrical and electronic parts such as wiring boards and insulating materials. It can apply to various plastic products, such as daily necessities, such as entertainment goods, bathroom goods, and big and small goods.

Example

Hereinafter, an Example demonstrates this invention. In the following Examples and Comparative Examples, "parts" means parts by weight unless otherwise specified. In addition, dicyclopentadiene is abbreviated as DCPD. In each of the following Examples and Comparative Examples, a metathesis polymerization catalyst represented by the following general formula (15) was used.

A. Examples 1-3 and Comparative Examples 1-6

In each of these examples, a DCPD resin liquid, which is a cycloolefin composition, was prepared using a reactive polysiloxane as a coupling agent, a filler was added thereto, and stirred at 400 rpm using a propeller blade for 5 minutes to give a compound (ie, a composite material). ) Was prepared.

The obtained compound was heated at 60 ° C. for 4 hours, and then cooled to about 35 ° C. and used. First, 0.10 part of metathesis polymerization catalyst was added to this compound, and after mixing, the compound was degassed under reduced pressure and the molding material which is a cycloolefin composition was obtained. The test piece was shape | molded using this molding material, and various characteristics were evaluated by the following method.

I. Flexural Characteristics

(a) Test piece manufacturing method

The above-mentioned molding material was cast in a mold having a thickness of 3 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) flexural test

A bending test piece having a width of 25 mm and a length of 80 mm was cut out of the flat plate, and a bending test (test speed 2 mm / min) was performed in accordance with JIS K7203. At this time, the bending strain was calculated | required by the following formula.

% Strain = 6dv / L ²

d: deformation amount at break (mm)

v: thickness of test piece (mm)

L: Distance between points (mm)

II. Water resistance

The retention ratio was determined from the strength of the dielectric breakdown before and after the pressure cooker test (PCT).

a) Test piece manufacturing method

The above-mentioned molding material was cast in a mold capable of flat plate having a thickness of 2 mm, and then the mold was heated in an oven for 5 hours at 40 ° C. for 2 hours at 130 ° C. to obtain a flat cured product.

(b) dielectric breakdown strength

It measured based on JISK6911. In addition, the conditions of PCT were temperature: 121 degreeC, pressure: 222 kPa, and time: 50 hours.

Table 1 shows the evaluation results. As can be seen from this table, the molded article obtained from the compound of each example using the reactive polysiloxane has a higher strain rate and toughness than the comparative examples. In addition, in each embodiment, there is no decrease in the dielectric breakdown strength after the PCT, and the water resistance is excellent.

<Example 1>

100 parts of pure PDPD with 98% purity, 2 parts of Smeizer BHT (trade name, antioxidant), triphenylphosphine (Hwagwang Pure Chemical Co., Ltd., reagent express) 0.05 parts, FZ3778 (manufactured by Japan Uniker Co., Ltd.) 2.0 parts of a brand name, ethoxymethylhydrogen polysiloxane) were added, and it decomposed, and the DCPD resin liquid was prepared. Thereafter, 150 parts of molten silica (average particle diameter: 5 µm) was added and mixed to obtain a compound.

<Example 2>

A compound was obtained in the same manner as in Example 1 except that 2.0 parts of MAC-2101 (polysiloxane having a trade name, epoxy and condensable silylalkyl group, manufactured by Nippon Uniker Co., Ltd.) was used instead of FZ3778.

<Example 3>

A compound was obtained in the same manner as in Example 1 except that 2.0 parts of polymer type silane coupling agent FZ3704 (trade name, polyethoxymethylsiloxane, manufactured by Nippon Uniker Co., Ltd.) was used instead of FZ3778.

Comparative Example 1

To 100 parts of DCPD having a purity of about 98%, 2 parts of smearizer BHT and 0.06 parts of triphenylphosphine (special grade) were added and dispersed to prepare a DCPD resin solution. Thereafter, 150 parts of molten silica (manufactured by Co., Ltd., average diameter of about 7 μm) was added and mixed to obtain a compound.

Comparative Example 2

2 parts of smistizer BHT, 0.06 parts of triphenylphosphine (Express) and 2.0 parts of silane coupling agent A-171 (trade name, vinyl trimethoxysilane manufactured by Nippon Uniker Co., Ltd.) were added to 100 parts of DCPD having a purity of about 98%. The mixture was dispersed to prepare a DCPD resin solution. Thereafter, 150 parts of molten silica (average particle size: about 5 mu m) was added and mixed to obtain a compound.

Comparative Example 3

A compound was obtained in the same manner as in Comparative Example 2 except that 2.0 parts of A-187 (trade name, γ-glycidoxypropyltrimethoxysilane, manufactured by Nippon Uniker Co., Ltd.) was used instead of A-171 as a silane coupling agent.

<Comparative Example 4>

A compound was obtained in the same manner as in Comparative Example 2 except that 2.0 parts of A-163 (trade name, manufactured by Nippon Uniker Co., Ltd., methyltrimethoxysilane) was used instead of A-171 as a silane coupling agent.

Comparative Example 5

A compound was obtained in the same manner as in Comparative Example 2 except that 2.0 parts of A-137 (trade name, manufactured by Japan Uniker Co., Ltd., n-octyltriethoxysilane) was used instead of A-171 as a silane coupling agent.

Comparative Example 6

A compound was obtained in the same manner as in Comparative Example 2 except that 2.0 parts of A-153 (Phenyltriethoxysilane, manufactured by Nippon Uniker Co., Ltd.) was used instead of A-171 as a silane coupling agent.

B. Example 4, Comparative Examples 7-8

In these Examples and Comparative Examples, DCPD resin was prepared by using DCPD and cyclooctadiene as cycloolefin monomers, a filler was added thereto, followed by stirring in the same manner as in Example 1 to prepare a compound.

The obtained compound was heated at 60 ° C. for 4 hours, and then cooled to about 35 ° C. and used. First, 0.15 parts of metathesis polymerization catalysts were added to this compound and mixed, and then the compound was degassed under reduced pressure to obtain a molding material.

The test piece was shape | molded using the obtained molding material, and various characteristics were evaluated by the following method. In addition, the manufacturing method of the test piece and the evaluation method of various characteristics were made the same as the case of Examples 1-3 mentioned above. The evaluation results are shown in Table 2.

<Example 4>

A compound was obtained in the same manner as in Example 1 except that 50 parts of DCPD having a purity of about 98% and 50 parts of cyclooctadiene (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.) were used instead of 100 parts of DCPD.

Comparative Example 7

A compound was obtained in the same manner as in Comparative Example 1 except that 100 parts of DCPD were used as the cycloolefin monomer, and 50 parts of cyclooctadiene (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

<Comparative Example 8>

A compound was obtained in the same manner as in Comparative Example 2 except that 100 parts of DCPD were used as the cycloolefin monomer and 50 parts of cyclooctadiene was used.

C. Examples 5-10, Comparative Examples 9-12

In each of these Examples, DCPD resin liquid was prepared using the metal containing coupling agent as a coupling agent, the filler was added to this, and it stirred like Example 1, and the compound was prepared.

0.12 parts of metathesis polymerization catalysts were added to this compound and mixed, and then the compound was degassed under reduced pressure to obtain a molding material.

The test piece was shape | molded using the obtained molding material, and various characteristics were evaluated by the following method. In addition, the manufacturing method of the test piece and the evaluation method of a bending characteristic were made the same as the case of Examples 1-3 mentioned above.

In addition, the reaction between the coupling agent and the filler was evaluated by decreasing the viscosity of the compound. Evaluation of the viscosity was evaluated based on JIS K6901 about the viscosity of the compound of 1 hour after preparation and the viscosity of the compound after being left to stand at 35 ° C for 20 hours. The measurement conditions were temperature: 35 degreeC, viscometer: BL type rotational viscometer, and rotation speed: 60 rpm.

Table 3 shows the results of the evaluation. As can be seen from Table 3, the bending property of the metal-containing coupling agent additives is superior to the additive-free products, and exhibits the same characteristics as those of the silica coupling agent. In addition, since the metal-containing coupling agent additive is faster in viscosity reduction than the silane coupling agent additive, it can be seen that the reaction between the coupling agent and the filler is faster.

Example 5

Fren37 KR55 (trade name, manufactured by Ajinomoto Co., Ltd., a titanium-based coupling agent having an aryl group, tetra (2,2-diaryloxymethyl-1-butyl) bis {di (tridecyl)} phosphite instead of FZ3778 as a coupling agent A compound was obtained in the same manner as in Example 1 except that 1.5 parts of titanate and bis (dioctylpyrophosphate) oxyacetate titanate) were used and the amount of molten silica added was 100 parts.

<Example 6>

A compound was obtained in the same manner as in Example 5 except that 1.5 parts of prenactal AL-M (trade name, acetoalkoxy aluminum diisopropylate, manufactured by Ajinomoto Co., Ltd.) was used instead of prenact KR55.

<Example 7>

A compound was obtained in the same manner as in Example 5 except that 1.0 part of Orcatics ZC-570 (zirconium acetylacetonate bisethyl acetonate, trade name manufactured by Song-Bon Pharmaceutical Co., Ltd.) was used instead of Frencact KR55.

<Example 8>

Preferred KR55 (0.5 parts) and A-163 (1.5 parts) were used in place of FZ3778, and the compound was obtained in the same manner as in Example 1 except that the amount of molten silica added was 100 parts.

Example 9

A compound was obtained in the same manner as in Example 8 except that the addition amount of prenact KR55 was 1.0 part, the addition amount of A-163 was 3.0 part, and the addition amount of molten silica was 200 part.

<Example 10>

A compound was prepared in the same manner as in Example 1 except that 1.0 part of Frenact KRTTS (trade name, Isopropyl triisostearoyl titanate manufactured by Ajinomoto Co., Ltd.) was used instead of FZ3778, and the amount of molten silica added was 100 parts. Got.

Comparative Example 9

A compound was obtained in the same manner as in Comparative Example 1 except that the addition amount of triphenylphosphine was 0.05 part, and the addition amount of molten silica was 100 part.

Comparative Example 10

A compound was obtained in the same manner as in Comparative Example 2 except that the addition amount of triphenylphosphine was 0.05 part, the addition amount of silane coupling agent A-171 was 1.5 part, and the addition amount of fused silica was 100 part.

Comparative Example 11

A compound was obtained in the same manner as in Comparative Example 5 except that the addition amount of triphenylphosphine was 0.05 part and the addition amount of molten silica was 100 part.

Comparative Example 12

A compound was obtained in the same manner as in Comparative Example 2 except that 3.0 parts of A-163 were used instead of A-171 as the silane coupling agent and the amount of molten silica added was 200 parts.

D. Examples 11-12 and Comparative Examples 13-14

In these Examples and Comparative Examples, the compound was prepared using calcium carbonate as the filler. In addition, stirring in the case of compound preparation was performed for 60 minutes at 2600 rpm using the turbine blade.

After 0.12 parts of metathesis polymerization catalysts were added to this compound and mixed, the compound was degassed under reduced pressure to obtain a molding material. The test piece was shape | molded using the obtained molding material, and various characteristics were evaluated by the following method. In addition, the manufacturing method of the test piece and the evaluation method of a bending characteristic were made the same as the case of Examples 1-3 mentioned above.

Table 4 shows the results of the evaluation. As can be seen from Table 4, the metal-containing coupling agent additives are superior to the additive-free flexural strength, and more excellent than the silane coupling agent additives.

<Example 11>

A compound was obtained in the same manner as in Example 5 except that the amount of Frencact KR55 added was 1.6 parts and 100 parts of NS400 (calcium carbonate, manufactured by Nihon Kogyo Co., Ltd.) was used instead of molten silica.

Comparative Example 12

A compound was obtained in the same manner as in Example 11 except that 0.8 parts of Prenact KRTTS was used instead of Prenact KR55.

Comparative Example 13

A compound was obtained in the same manner as in Comparative Example 9 except that 100 parts of NS400 (calcium carbonate, manufactured by Ildong Chemical Co., Ltd.) was used instead of fused silica.

Comparative Example 14

A compound was obtained in the same manner as in Comparative Example 10 except that 100 parts of NS400 (calcium carbonate, manufactured by Ildong Chemical Co., Ltd.) was used instead of fused silica.

According to the cycloolefin composition and the molding material of the present invention, it is possible to suppress a decrease in toughness (particularly strain in bending test) without deteriorating water resistance, electrical insulation and mechanical properties. The molded article obtained from the cycloolefin composition and the molding material of the present invention produces excellent water resistance, self-resistance, mechanical properties, and electrical properties of the cycloolefin polymer, for example, a septic tank, a bath, a kitchen top plate, a tank, a unit bath, a wall panel, a cruise ship, It can be used for applications such as sewage tanks, drain pipes, wave plates, wiring boards, molded articles such as insulating materials, electrical parts, and electronic parts.

Claims (14)

In the cycloolefin composition containing a metathesis-polymerizable cycloolefin monomer, a coupling agent, and a metathesis polymerization catalyst, A cycloolefin composition comprising at least one of a metal-containing coupling agent and a reactive polysiloxane as the coupling agent. The method of claim 1, wherein the coupling agent A cycloolefin composition comprising at least one selected from a metal-containing coupling agent comprising any one of titanium, aluminum, zirconium, iron, calcium, magnesium and zinc. The method of claim 1, wherein the coupling agent Tetra (2,2-diaryloxymethyl-1-butyl) bis {di (tridecyl)} phosphite titanate, isopropyltriisostearoyl titanate, acetoalkoxyaluminum diisopropylate and zirconiumacetylacetonate A cycloolefin composition comprising at least one of bisethylacetonate. The method of claim 1, wherein the coupling agent A cycloolefin composition comprising a reactive polysiloxane represented by the following general formula (1). Wherein each R represents a hydrogen atom, a monovalent hydrocarbon group or a halogenated alkyl group selected independently from each other, Y represents an organic reactive functional group represented by the following general formula (4), -R ¹ -X... (4) (Wherein R ¹ represents a direct bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and X represents a functional group having organic reactivity). Z represents a hydrolyzable group or a condensable silylalkyl group represented by the following general formula (5), (Wherein R ² represents an alkylene group having 2 to 5 carbon atoms, R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms independently selected from each other, and r is 2 or 3) Q represents a polyoxyalkylene group represented by the following general formula (6), (Wherein R ⁵ represents a hydrogen atom, an acyl group or a monovalent hydrocarbon group, p is 0 or a positive integer, m and n are a positive integer of 0 or 150 or less, and m + n is an integer of 1 to 150) to be.) M ¹ independently of one another represents a group selected from said R, Y, Z and Q, a is an integer of 0 to 500, b is an integer of 0 to 200 (however, when b is 0, M ¹ is Y and both d and e are integers of 1 or more), and d is 0 to 200 Is an integer (when d is 0, M ¹ is Z, and b and neither is an integer of 1 or more), and e is an integer of 0 to 200 (when e is 0, M ¹ is Q, and b and d are all integers of 1 or more). The method of claim 1, wherein the coupling agent The cycloolefin composition characterized by including the reactive polysiloxane represented by following General formula (2). Here, each R represents a hydrogen atom, a monovalent hydrocarbon group or a halogenated alkyl group selected independently from each other, Y represents an organic reactive functional group represented by the following general formula (4), -R ¹ -X... (4) (However, R ¹ represents a direct bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and X represents a functional group having organic reactivity.) Z represents a hydrolyzable group or a condensable silylalkyl group represented by the following general formula (5), (However, R ² represents an alkylene group having 2 to 5 carbon atoms, R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms independently selected from each other, and r is 2 or 3. M ² independently of one another represents a group selected from R, Y and Z, f is an integer from 0~500, g is an integer from 0 to 200 (when g is 0, and M ² is Y, In addition, h is an integer more than 1), h is an integer from 0 to 200 (the h In the case of 0, M ² is Z, and f is an integer of 1 or more). The cycloolefin composition according to claim 1, wherein the coupling agent comprises a reactive polysiloxane represented by the following general formula (3). Here, each R represents a hydrogen atom, a monovalent hydrocarbon group or a halogenated alkyl group selected independently from each other, Z represents a hydrolyzable group or a condensable silylalkyl group represented by the following general formula (5), (However, R ² represents an alkylene group having 2 to 5 carbon atoms, R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms independently selected from each other, and r is 2 or 3.) M ³ independently represents a group selected from R and Y, j is an integer of 0 to 500, k is an integer of 0 to 500 (M ³ is Z when k is 0). The cycloolefin composition according to claim 1, wherein the metathesis polymerization catalyst is a ruthenium compound. The cycloolefin composition according to claim 1, wherein the metathesis polymerization catalyst is a compound represented by the following general formula (7) or (8). (However, M represents ruthenium or osmium, X ¹ and X ² each represent an anionic ligand, L ¹ and L ² each represent a neutral ligand, Q ¹ and Q ² each represent a group independently selected from hydrogen, an alkyl group, an alkyl group having a substituent, an alkenyl group, an alkenyl group having a substituent, an aromatic group and an aromatic group having a substituent.) The cycloolefin composition according to claim 8, wherein the metathesis catalyst is a compound represented by the following general formula (9). (However, R ⁵ and R ⁶ are each an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group, a carboxylate group having 1 to 18 carbon atoms, and 1 to 18 carbon atoms). Alkoxyl group, C2-C18 alkenyloxy group, C2-C18 alkynyloxy group, C2-C18 aryloxy group, C2-C18 alkoxycarbonyl group, C1-C18 alkylthio group, C1-C1 Group independently selected from an alkylsulfonyl group having from 18 and an alkylsulfinyl group having from 1 to 18 carbon atoms, R ⁷ represents a group selected from hydrogen, an aryl group and an alkyl group having 1 to 18 carbon atoms.) The cycloolefin composition according to claim 1, further comprising a filler, wherein the filler is at least one selected from glass, silica, alumina, magnesium hydroxide, aluminum hydroxide, and silicon. The cycloolefin composition according to claim 1, wherein the cycloolefin monomers include dicyclopentadiene. In the manufacturing method of the cycloolefin composition containing the process of mixing a metathesis-polymerizable cycloolefin monomer, a coupling agent, and a metathesis polymerization catalyst, The coupling agent comprises at least one of a metal-containing coupling agent and a reactive polysiloxane. A molding material comprising the cycloolefin composition of claim 1. It is obtained by hardening | curing the molding material of Claim 13, The molded object which is a hardened | cured material.