Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
  • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
  • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
  • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2265—Carbenes or carbynes, i.e.(image)
  • B01J31/2269—Heterocyclic carbenes
  • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2265—Carbenes or carbynes, i.e.(image)
  • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
  • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
  • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/82—Metals of the platinum group
  • B01J2531/821—Ruthenium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/40—Polymerisation processes
  • C08G2261/41—Organometallic coupling reactions
  • C08G2261/418—Ring opening metathesis polymerisation [ROMP]

Definitions

• the present invention relates to a polymerizable composition that allows the curing time to be controlled within an appropriate range, achieving excellent workability, and a norbornene-based resin obtained using such a polymerizable composition.
• Norbornene resins obtained by ring-opening polymerization of norbornene monomers are known to have excellent mechanical strength, heat resistance, low moisture absorption, and dielectric properties, and are used for a variety of purposes.
• Patent Document 1 discloses a ruthenium carbene complex having a phosphine as a ligand as a metathesis polymerization catalyst used for ring-opening polymerization of norbornene-based monomers. Patent Document 1 also discloses a polymerizable composition using such a ruthenium carbene complex.
• the polymerizable composition using the ruthenium carbene complex disclosed in Patent Document 1 as a polymerization catalyst has the problem that the curing time is short and workability is poor when filling a mold, etc.
• the present invention aims to provide a polymerizable composition that allows the curing time to be controlled within an appropriate range, achieving excellent workability.
• the inventors conducted research to achieve the above object, and discovered that by blending a specific amount of a coordinating compound containing a phosphorus atom in a polymerizable composition containing a norbornene monomer and a ruthenium carbene complex having a specific phosphine ligand as a metathesis polymerization catalyst, the curing time of the polymerizable composition can be controlled within an appropriate range, and excellent workability can be achieved, which led to the completion of the present invention.
• a polymerizable composition comprising a norbornene-based monomer, a metathesis polymerization catalyst, and a coordination compound containing a phosphorus atom
• the metathesis polymerization catalyst is a ruthenium carbene complex represented by the following general formula (1) or (2):
• the polymerizable composition has a phosphorus atom-containing coordination compound content of 170 to 2,000 moles, calculated as phosphorus atoms, per mole of ruthenium atoms in the metathesis polymerization catalyst.
• R 1 and R 2 are each independently a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom; these groups may have a substituent and may be bonded to each other to form a ring.
• X 1 and X 2 are each independently an arbitrary anionic ligand.
• L 1 and L 2 are a heteroatom-containing carbene compound or a phosphine, and at least one of L 1 and L 2 is a phosphine.
• L 1 is a compound represented by the following general formula (3) or (4)
• L 2 is a phosphine:
• R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom, and these groups may have a substituent and may be bonded to each other to form a ring.
• the phosphine is a trialkylphosphine which
• the present invention provides a polymerizable composition that allows the curing time to be controlled within an appropriate range, realizing excellent workability, and a norbornene-based resin obtained using such a polymerizable composition.
• the polymerizable composition of the present invention is a polymerizable composition comprising a norbornene-based monomer, a metathesis polymerization catalyst, and a coordination compound containing a phosphorus atom
• the metathesis polymerization catalyst is a ruthenium carbene complex represented by general formula (1) or general formula (2) described later,
• the content of the phosphorus atom-containing coordination compound in the polymerizable composition is 170 to 2,000 moles, calculated as phosphorus atoms, per mole of ruthenium atoms in the metathesis polymerization catalyst.
• the norbornene-based monomer may be any compound having a norbornene ring structure, and is not particularly limited thereto.
• Examples of the norbornene-based monomer include bicyclic monomers such as norbornene and norbornadiene; tricyclic monomers such as dicyclopentadiene; tetracyclic monomers such as tetracyclododecene; pentacyclic monomers such as tricyclopentadiene; heptacyclic monomers such as tetracyclopentadiene; and derivatives of these monomers having an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkylidene group having 1 to 10 carbon atoms, an epoxy group, or a (meth)acrylic group [CH 2 ⁇ CHCH 2 - and/or CH 2 ⁇ C(CH 3 )CH 2 -].
• (meth)acrylic group refers to an acrylic group and/or a methacrylic group (hereinafter, the same applies to "(meth)acryloyl group” and the like).
• the norbornene-based monomers may be used alone or in combination of two or more kinds.
• the norbornene-based monomer the tricyclic compound is preferable, and dicyclopentadiene is particularly preferable, from the viewpoint of further enhancing the effects of the present invention.
• the norbornene-based monomer used preferably contains the tricyclic compound, particularly dicyclopentadiene, in an amount of 50 mass% or more.
• the content of the norbornene-based monomer in the polymerizable composition of the present invention is not particularly limited, but is preferably 80 to 100 mass%, preferably 80 to 95 mass%, more preferably 85 to 92 mass%, and even more preferably 87 to 90 mass%, of the total 100 mass% of polymerizable monomers contained in the polymerizable composition.
• the strength of the obtained norbornene-based resin can be further increased.
• a monocyclic cycloolefin may further be used as a polymerizable monomer contained in the polymerizable composition.
• monocyclic cycloolefins include, but are not limited to, cyclobutene, cyclopentene, cyclohexene, cyclooctene, cyclododecene, cyclopentadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, and derivatives thereof having an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkylidene group having 1 to 10 carbon atoms, an epoxy group, or a (meth)acrylic group.
• the monocyclic cycloolefins can be used alone or in combination of two or more kinds.
• the polymerizable composition of the present invention may contain, in addition to the norbornene monomer and the monocyclic cycloolefin used as necessary, other polymerizable monomers that are polymerizable with these.
• other polymerizable monomers include other cycloolefin monomers and (meth)acrylate monomers such as phenoxyethylene glycol (meth)acrylate.
• the content of polymerizable monomers other than norbornene-based monomers in the polymerizable composition of the present invention is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, based on 100% by mass of the total polymerizable monomers contained in the polymerizable composition, and may be 0% by mass.
• the lower limit of the total polymerizable monomer content in the polymerizable composition of the present invention can be, based on 100% by mass of the entire polymerizable composition, preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 50% by mass or more, and particularly preferably 80% by mass or more.
• the upper limit of the total polymerizable monomer content can be, based on 100% by mass of the entire polymerizable composition, preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 95% by mass or less, even more preferably 93% by mass or less, and particularly preferably 90% by mass or less.
• the metathesis polymerization catalyst used in the present invention is a ruthenium carbene complex represented by the following general formula (1) or (2).
• R1 and R2 are each independently a hydrogen atom, a halogen atom, or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom, and these groups may have a substituent or may be bonded to each other to form a ring.
• An example of R1 and R2 bonded to each other to form a ring is an indenylidene group which may have a substituent, such as a phenylindenylidene group.
• organic groups having 1 to 20 carbon atoms which may contain a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom or silicon atom
• alkyl groups having 1 to 20 carbon atoms alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, alkenyloxy groups having 2 to 20 carbon atoms, alkynyloxy groups having 2 to 20 carbon atoms, aryloxy groups having 6 to 20 carbon atoms, alkylthio groups having 1 to 8 carbon atoms, carbonyloxy groups, alkoxycarbonyl groups having 1 to 20 carbon atoms, alkylsulfonyl groups having 1 to 20 carbon atoms, alkylsulfinyl groups having 1 to 20 carbon atoms, alkylsulfonic acid groups having 1 to 20 carbon atoms,
• These organic groups having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom, may have a substituent.
• substituents include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms.
• X1 and X2 each independently represent any anionic ligand.
• the anionic ligand is a ligand that has a negative charge when separated from a central metal atom, and examples of the anionic ligand include a halogen atom, a diketonate group, a substituted cyclopentadienyl group, an alkoxyl group, an aryloxy group, and a carboxyl group.
• L1 and L2 are heteroatom-containing carbene compounds or phosphines, and at least one of L1 and L2 is a phosphine.
• heteroatom-containing carbene compound a compound represented by the following general formula (3) or (4) is preferable, and from the viewpoint of improving catalytic activity, a compound represented by the following general formula (3) is more preferable.
• R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom, a halogen atom, or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom.
• Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom are the same as those in the above general formulas (1) and (2).
• R 3 , R 4 , R 5 , R 6 , R 7 and R 8 may be bonded to each other in any combination to form a ring.
• R5 , R6 , R7 , and R8 in the above general formula (3) and R5 and R6 in the above general formula (4) are hydrogen atoms.
• R3 and R4 are preferably an aryl group which may have a substituent, more preferably a phenyl group having an alkyl group having 1 to 10 carbon atoms as a substituent, and further preferably a mesityl group.
• Phosphines are not particularly limited, but from the viewpoint of catalytic activity, trialkylphosphines which may have a substituent or triarylphosphines which may have a substituent are included, with trialkylphosphines which may have a substituent being preferred, and trialkylphosphines which do not have a substituent being more preferred.
• trialkylphosphines which do not have a substituent include trimethylphosphine, triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, tri-n-octadecylphosphine, tricyclopentylphosphine, and tricyclohexylphosphine, and among these, tricycloalkylphosphines are more preferred, with tricyclohexylphosphine being particularly preferred.
• R 1 , R 2 , X 1 , X 2 , L 1 and L 2 may each be alone and/or bonded to each other in any combination to form a multidentate chelating ligand.
• the metathesis polymerization catalyst used in the present invention is preferably one in which L1 is a compound represented by the above general formula (3) or (4) and L2 is a phosphine.
• L1 is a compound represented by the above general formula (3) or (4)
• L2 is a phosphine.
• Specific examples of the compound represented by the above general formula (3) or (4) include 1,3-di(1-adamantyl)imidazolidin-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1,3-di(1-phenylethyl)-4-imidazolin-2-ylidene, 1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazol-5-ylidene, 1,3-dicyclohexylhexahydropi
• Examples of the imididine-2-ylidene include N,N,N',N'-tetraiso
• the metathesis polymerization catalyst used in the present invention is a ruthenium carbene complex represented by the above general formula (1) or (2), and is preferably a ruthenium carbene complex represented by the above general formula (1).
• Specific examples of the metathesis polymerization catalyst represented by the above general formula (1) include benzylidene(1,3-dimesitylimidazolidin-2-ylidene)(tricyclohexylphosphine)ruthenium dichloride, (1,3-dimesitylimidazolidin-2-ylidene)(3-methyl-2-buten-1-ylidene)(tricyclopentylphosphine)ruthenium dichloride, benzylidene(1,3-dimesityl-octahydrobenzimidazol-2-ylidene)(tricyclohexylphosphine)ruthenium dichloride, benzylidene[1,3-di(1-phenylethyl)-4-imi
• benzylidene (1,3-dimesitylimidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and (1,3-dimesitylimidazolidin-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclohexylphosphine) ruthenium dichloride are preferred from the viewpoint that the effect of the present invention is more pronounced.
• the content of the metathesis polymerization catalyst is preferably 0.005 millimoles or more, more preferably 0.01 to 50 millimoles, even more preferably 0.015 to 20 millimoles, and particularly preferably 1 to 3 millimoles, per mole of the total amount of polymerizable monomers used in the reaction.
• the content of the metathesis polymerization catalyst, calculated on a weight basis, is preferably 0.004 parts by mass or more, more preferably 0.008 to 45 parts by mass, even more preferably 0.012 to 20 parts by mass, and particularly preferably 0.8 to 2.5 parts by mass, per 10,000 parts by mass of the total amount of polymerizable monomers used in the reaction.
• the polymerizable composition of the present invention contains a coordination compound containing a phosphorus atom, and the content of the coordination compound containing a phosphorus atom is 170 to 2000 moles of phosphorus atoms per mole of ruthenium atoms in the metathesis polymerization catalyst.
• the coordination compound containing a phosphorus atom in the polymerizable composition in the above-mentioned specific amount, even when the above-mentioned specific ruthenium carbene complex is used as the metathesis polymerization catalyst, the curing time can be controlled within an appropriate range, thereby realizing excellent workability (excellent workability when filling a mold, etc.).
• the phosphorus-atom-containing coordinating compound may be any compound that contains a phosphorus atom and has coordinating properties and thus acts as a Lewis base. From the viewpoint of further enhancing the effects of the present invention, however, a compound represented by the following general formula (5) is preferred.
• R 9 to R 11 are each independently an alkyl group which may have a substituent, or an aryl group which may have a substituent.
• an aryl group which may have a substituent is preferable, and examples of the aryl group which may have a substituent include an unsubstituted aryl group such as a phenyl group, and an aryl group having an electron-donating group as a substituent such as a tolyl group, a methoxyphenyl group, and an ethoxyphenyl group.
• R 9 to R 11 may be the same group or different groups from each other, or may be a polyvalent phosphine formed via an alkylene group.
• the polyvalent phosphine is preferably, for example, a compound represented by the following general formula:
• R 12 , R 13 , R 15 , and R 16 are each independently an alkyl group which may have a substituent, or an aryl group which may have a substituent
• R 14 is an alkylene group which may have a substituent
• n is an integer of 2 or more.
• R 12 , R 13 , R 15 , and R 16 are preferably aryl groups which may have a substituent, and examples of the aryl group which may have a substituent include unsubstituted aryl groups such as phenyl groups, and aryl groups having an electron donating group as a substituent such as tolyl groups, methoxyphenyl groups, and ethoxyphenyl groups.
• R 14 is preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 2 to 5 carbon atoms.
• n is preferably 2 to 6, more preferably 2 to 6, and particularly preferably 2.
• the compound represented by the above general formula (5) is not particularly limited, but examples thereof include triphenylphosphine, tri-p-tolylphosphine, tri-m-tolylphosphine, tri-o-tolylphosphine, cyclohexyldiphenylphosphine, trimethoxyphenylphosphine, triethoxyphenylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, and 1,4-bis(diphenylphosphinobutane).
• the compound represented by the above general formula (5) may be used alone or in combination of two or more.
• triphenylphosphine, trimethoxyphenylphosphine, 1,2-bis(diphenylphosphino)ethane, and 1,4-bis(diphenylphosphinobutane) are preferred, and it is more preferred to use triphenylphosphine and trimethoxyphenylphosphine in combination.
• the molar ratio of "triphenylphosphine:trimethoxyphenylphosphine" calculated in terms of phosphorus atoms is preferably 1:2 to 10:1, more preferably 1:1 to 5:1.
• the content of the phosphorus atom-containing coordination compound in the polymerizable composition of the present invention is 170 to 2000 moles, preferably 180 to 850 moles, and more preferably 190 to 700 moles, calculated as phosphorus atoms, per mole of ruthenium atoms in the metathesis polymerization catalyst.
• the content of the phosphorus atom-containing coordination compound in the polymerizable composition of the present invention, calculated as weight, is preferably 54 to 320 parts by mass, more preferably 55 to 270 parts by mass, and even more preferably 56 to 220 parts by mass, per part by mass of the metathesis polymerization catalyst.
• the content of the phosphorus atom-containing coordination compound is too low, the curing time will be short and the composition will be difficult to handle, while if the content of the phosphorus atom-containing coordination compound is too high, the catalytic activity will be insufficient and the polymerization reaction may not proceed sufficiently.
• the polymerizable composition of the present invention may also contain a radical generator, a diisocyanate compound, a polyfunctional (meth)acrylate compound, a coupling agent, and other optional components, as desired.
• the radical generator generates radicals when heated, which has the effect of inducing a crosslinking reaction in norbornene-based resins.
• the sites where the radical generator induces the crosslinking reaction are mainly the carbon-carbon double bonds contained in norbornene-based resins, but crosslinking can also occur in saturated bond portions.
• Examples of radical generators include organic peroxides, diazo compounds, and non-polar radical generators.
• the content of the radical generator in the composite composition of the present invention is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total amount of polymerizable monomers.
• diisocyanate compound examples include 4,4'-methylene diphenyl diisocyanate (MDI), toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, and 4,4'-diisocyanate dibenzyl ether.
• MDI 4,4'-methylene diphenyl diisocyanate
• toluene-2,4-diisocyanate 4-me
• diisocyanate examples include aromatic diisocyanate compounds such as benzyl; aliphatic diisocyanate compounds such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate; alicyclic diisocyanate compounds such as 4-cyclohexylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI, and hydrogenated XDI, and polyurethane prepolymers obtained by reacting these diisocyanate compounds with low molecular weight polyols or polyamines so that the terminals are isocyanate.
• aromatic diisocyanate compounds such as benzyl
• aliphatic diisocyanate compounds such as methylene diisocyanate, 1,4-te
• conventionally known compounds having a polyfunctional isocyanate group which are made into an isocyanurate, biuret, adduct, or polymeric form, can be used without any particular limitation.
• examples of such compounds include a dimer of 2,4-tolylene diisocyanate, triphenylmethane triisocyanate, tris-(p-isocyanatophenyl)thiophosphite, polyfunctional aromatic isocyanate compounds, polyfunctional aromatic aliphatic isocyanate compounds, polyfunctional aliphatic isocyanate compounds, fatty acid modified polyfunctional aliphatic isocyanate compounds, polyfunctional blocked isocyanate compounds such as blocked polyfunctional aliphatic isocyanate compounds, polyisocyanate prepolymers, etc.
• aromatic diisocyanate compounds aliphatic diisocyanate compounds, and alicyclic diisocyanate compounds, which are polyfunctional unblocked isocyanate compounds, are preferably used because of their excellent availability and ease of handling. These compounds may be used alone or in combination of two or more.
• a polyfunctional blocked isocyanate compound is one in which at least two isocyanate groups in the molecule are reacted with an active hydrogen-containing compound to render the compound inactive at room temperature.
• the isocyanate compound generally has a structure in which the isocyanate groups are masked with a blocking agent such as alcohols, phenols, ⁇ -caprolactam, oximes, and active methylene compounds.
• Polyfunctional blocked isocyanate compounds generally have excellent storage stability because they do not react at room temperature, but the isocyanate groups are usually regenerated by heating at 140 to 200°C, and they can exhibit excellent reactivity.
• the diisocyanate compounds may be used alone or in combination of two or more.
• the amount of the diisocyanate compound in the polymerizable composition of the present invention is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 10 parts by mass, per 100 parts by mass of the total amount of polymerizable monomers used in the reaction.
• polyfunctional (meth)acrylate compounds may be used from the viewpoint of further improving the adhesive strength to other materials.
• a polyfunctional (meth)acrylate compound together with a diisocyanate compound it is presumed that the active hydrogen reactive group of the diisocyanate compound forms a chemical bond with the hydroxyl group present in the polyfunctional (meth)acrylate compound, thereby further increasing the adhesive strength to other materials.
• Preferred examples of polyfunctional (meth)acrylate compounds include ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and neopentyl glycol dimethacrylate.
• the polyfunctional (meth)acrylate compounds may be used alone or in combination of two or more.
• the amount of the polyfunctional (meth)acrylate compound in the polymerizable composition is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 10 parts by mass, per 100 parts by mass of the total amount of polymerizable monomers used in the reaction.
• a silane coupling agent having at least one hydrocarbon group with a norbornene structure is preferred from the viewpoint of improving adhesion to other materials.
• silane coupling agents include bicycloheptenyl trimethoxysilane, bicycloheptenyl triethoxysilane, bicycloheptenyl ethyl trimethoxysilane, bicycloheptenyl ethyl triethoxysilane, bicycloheptenyl hexyl trimethoxysilane, and bicycloheptenyl hexyl triethoxysilane, but preferred are bicycloheptenyl ethyl trimethoxysilane, bicycloheptenyl ethyl triethoxysilane, bicycloheptenyl hexyl trimethoxysilane, and bicycloheptenyl hexyl triethoxysilane, more preferred are bicycloheptenyl ethyl trimethoxysilane and bicycloheptenyl ethyl triethoxysi
• the content of the silane coupling agent having at least one hydrocarbon group having a norbornene structure in the polymerizable composition of the present invention is preferably 0.1 to 5 mass %, more preferably 0.3 to 2 mass %, and even more preferably 0.5 to 1 mass %.
• the polymerizable composition of the present invention may also contain a silane coupling agent that does not have a hydrocarbon group having a norbornene structure, or a coupling agent other than a silane coupling agent, such as a thiol coupling agent, an aluminate coupling agent, a titanate coupling agent, or a fatty acid ester.
• a silane coupling agent that does not have a hydrocarbon group having a norbornene structure
• a coupling agent other than a silane coupling agent such as a thiol coupling agent, an aluminate coupling agent, a titanate coupling agent, or a fatty acid ester.
• activators include activators, elastomers, antioxidants (anti-aging agents), colorants, light stabilizers, flame retardants, etc.
• the activator is a compound that acts as a co-catalyst for the metathesis polymerization catalyst described above and improves the polymerization activity of the catalyst.
• activators that can be used include alkylaluminum halides such as ethylaluminum dichloride and diethylaluminum chloride; alkoxyalkylaluminum halides in which part of the alkyl groups of these alkylaluminum halides are replaced with alkoxy groups; and organotin compounds.
• the amount of activator used is preferably 0.1 to 100 moles, and more preferably 1 to 10 moles, per mole of the total metathesis polymerization catalyst used in the polymerizable composition.
• elastomers examples include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), ethylene-propylene-diene terpolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), and hydrogenated versions of these.
• SBR styrene-butadiene copolymer
• SBS styrene-butadiene-styrene copolymer
• SIS styrene-isoprene-styrene copolymer
• EPDM ethylene-propylene-diene terpolymer
• EVA ethylene-vinyl acetate copolymer
• the impact resistance of the norbornene resin formed by bulk polymerization of the composition can be improved by adding an elastomer.
• the amount of elastomer used is preferably 0.5 to 20 parts by mass, more preferably 2 to 10 parts by mass, based on 100 parts by mass of the total amount of polymerizable monomers in the polymerizable composition.
• Antioxidants include various types of antioxidants for plastics and rubber, such as phenol-based, phosphorus-based, and amine-based antioxidants.
• Dyes, pigments, etc. are used as colorants. There are many types of dyes, and known dyes can be appropriately selected and used. Examples of pigments include carbon black, graphite, yellow lead, yellow iron oxide, titanium dioxide, zinc oxide, trilead tetroxide, red lead, chromium oxide, iron blue, and titanium black.
• light stabilizers examples include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, salicylate-based UV absorbers, cyanoacrylate-based UV absorbers, oxanilide-based UV absorbers, hindered amine-based UV absorbers, and benzoate-based UV absorbers.
• Flame retardants include phosphorus-based flame retardants, nitrogen-based flame retardants, halogen-based flame retardants, and metal hydroxide-based flame retardants such as aluminum hydroxide or magnesium hydroxide.
• the polymerizable composition of the present invention may contain a filler as an optional component.
• a filler can be used as the filler, and although there are no particular limitations, it is preferable to use a particulate inorganic filler.
• the particulate inorganic filler preferably has an aspect ratio of 1 to 2, and more preferably has an aspect ratio of 1 to 1.5.
• the 50% volume cumulative diameter of the particulate inorganic filler is preferably 0.1 to 50 ⁇ m, more preferably 1 to 30 ⁇ m, and particularly preferably 1 to 10 ⁇ m.
• the aspect ratio refers to the ratio of the average major axis diameter of the filler to the 50% volume cumulative diameter.
• the average major axis diameter is the number-average major axis diameter calculated as the arithmetic mean value of the major axis diameters of 100 fillers randomly selected from an optical microscope photograph.
• the 50% volume cumulative diameter is a value determined by measuring the particle size distribution using an X-ray transmission method.
• particulate inorganic fillers include calcium carbonate, calcium hydroxide, calcium silicate, calcium sulfate, aluminum hydroxide, magnesium hydroxide, titanium oxide, zinc oxide, barium titanate, silica, alumina, gadolinia, carbon black, graphite, antimony oxide, red phosphorus, various metal powders, metal alloy powders, clay, various ferrites, hydrotalcite, etc.
• magnesium hydroxide, aluminum hydroxide, silica, and alumina are preferred, with aluminum hydroxide and silica being particularly preferred.
• the particulate inorganic filler may have its surface hydrophobized.
• a hydrophobized particulate inorganic filler By using a hydrophobized particulate inorganic filler, aggregation and sedimentation of the particulate inorganic filler in the polymerizable composition can be prevented, and the particulate inorganic filler can be uniformly dispersed in the resulting norbornene-based resin. As a result, the strength of the norbornene-based resin can be further increased.
• the treatment agent used for the hydrophobization treatment include silane coupling agents such as vinyl silane, titanate coupling agents, aluminum coupling agents, fatty acids such as stearic acid, oils and fats, surfactants, waxes, etc.
• the treatment agent used for the hydrophobization treatment may be reacted with the particulate inorganic filler in advance to hydrophobize the surface of the particulate inorganic filler, or the treatment agent used for the hydrophobization treatment may be blended into the polymer composition without reacting with the particulate inorganic filler in advance, and the surface of the particulate inorganic filler may be hydrophobized in the polymer composition.
• the amount of particulate inorganic filler in the polymerizable composition of the present invention is preferably 10 to 1,000 parts by mass, and more preferably 100 to 500 parts by mass, per 100 parts by mass of the total amount of polymerizable monomers.
• the polymerizable composition of the present invention may contain a fibrous inorganic filler in addition to the particulate inorganic filler.
• the fibrous inorganic filler preferably has an aspect ratio of 5 to 100, and more preferably has an aspect ratio of 10 to 50.
• the 50% cumulative volume diameter of the fibrous inorganic filler is preferably 0.1 to 50 ⁇ m, and more preferably 1 to 30 ⁇ m.
• fibrous inorganic fillers include glass fibers, wollastonite, potassium titanate, zonolite, basic magnesium sulfate, aluminum borate, tetrapod-type zinc oxide, gypsum fibers, phosphate fibers, alumina fibers, whisker-like calcium carbonate, and whisker-like boehmite. Of these, wollastonite and whisker-like calcium carbonate are preferred. Furthermore, the fibrous inorganic filler may have its surface hydrophobized, similar to the particulate inorganic filler described above.
• the polymerizable composition of the present invention is prepared by appropriately mixing the above-mentioned components according to a known method.
• the polymerizable composition of the present invention may be prepared by preparing two or more premixed liquids and mixing the two or more premixed liquids using a mixing device or the like just before making the norbornene-based resin.
• the premixed liquid does not undergo bulk polymerization with only one liquid, but the above-mentioned components are prepared by dividing them into two or more liquids so that when all the liquids are mixed together, a polymerizable composition containing each component in a predetermined ratio (total of the contents of each component is 100% by mass) is obtained.
• Such combinations of two or more reaction stock liquids include the following two types (a) and (b), depending on the type of metathesis polymerization catalyst used.
• a premixed liquid (liquid A) containing a polymerizable monomer containing a norbornene-based monomer and an activator, and a premixed liquid (liquid B) containing a polymerizable monomer containing a norbornene-based monomer and a metathesis polymerization catalyst are used and mixed to obtain a polymerizable composition.
• a premixed liquid (liquid C) containing a polymerizable monomer containing a norbornene-based monomer and not containing a metathesis polymerization catalyst or an activator may be used in combination.
• the phosphorus-containing coordination compound may be contained in any of the premixed liquids, but from the viewpoint of increasing the storage stability of the metathesis polymerization catalyst, it is preferable to contain it at least in the premixed liquid (liquid B).
• a polymerizable composition can be obtained by mixing a premixed liquid (i) containing a polymerizable monomer including a norbornene-based monomer with a premixed liquid (ii) containing a metathesis polymerization catalyst.
• the premixed liquid (ii) is usually a liquid in which the metathesis polymerization catalyst is dissolved or dispersed in a small amount of an inert solvent.
• solvents examples include aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and trimethylbenzene; ketones such as methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and 4-hydroxy-4-methyl-2-pentanone; cyclic ethers such as tetrahydrofuran; diethyl ether, dichloromethane, dimethyl sulfoxide, and ethyl acetate.
• aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and trimethylbenzene
• ketones such as methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and 4-hydroxy-4-methyl-2-pentanone
• cyclic ethers such as tetrahydrofuran
• diethyl ether dichloromethane
• the phosphorus atom-containing coordination compound may be contained in either of the premixed liquids.
• the content ratio of the phosphorus atom-containing coordination compound is preferably 1:0.01 to 1:10, more preferably 1:0.1 to 1:9, and even more preferably 1:0.2 to 1:8, in terms of the weight ratio of "the amount of the phosphorus atom-containing coordination compound contained in the premixed liquid (i) (monomer liquid): the amount of the phosphorus atom-containing coordination compound contained in the premixed liquid (ii) (catalyst liquid)".
• Optional components such as radical generators, diisocyanate compounds, and polyfunctional (meth)acrylate compounds may be included in any of the premixed liquids, or may be added in the form of a mixed liquid other than the premixed liquids.
• the above premixed liquid can be mixed as is, or can be mixed using a mixing device such as an impingement mixer commonly used in reaction injection molding, or a low-pressure mixer such as a dynamic mixer or static mixer.
• a mixing device such as an impingement mixer commonly used in reaction injection molding, or a low-pressure mixer such as a dynamic mixer or static mixer.
• the norbornene-based resin of the present invention is obtained by bulk polymerization of the above-mentioned polymerizable composition of the present invention.
• the norbornene resin of the present invention can be produced, for example, by introducing the two or more premixed liquids described above separately into an impingement mixer, mixing them instantaneously with a mixing head, and then bulk polymerizing them in a mold or on a substrate.
• the mold is not particularly limited, but for example, a metal mold formed of a male mold and a female mold can be used.
• the mold used does not necessarily have to be a highly rigid and expensive mold, and is not limited to a metal mold, but a resin mold or a simple formwork can be used.
• the material is not particularly limited, but examples include steel, aluminum, zinc alloy, nickel, copper, chromium, etc., and the mold may be manufactured by any method such as casting, forging, thermal spraying, electroforming, etc., or may be plated.
• the structure of the mold should be determined taking into consideration the pressure when the polymerizable composition is injected into the mold.
• the clamping pressure of the mold is usually about 0.1 to 9.8 MPa in gauge pressure.
• the mold temperature may be appropriately selected depending on the type of norbornene-based monomer used, but is preferably at least 5° C. higher than the freezing point of the norbornene-based monomer, and more preferably at least 10° C. higher than the freezing point.
• the heating temperature is preferably 90 to 200°C, more preferably 100 to 170°C, and even more preferably 110 to 150°C.
• Methods for adjusting the mold temperature include, for example, adjusting the mold temperature with a heater; adjusting the temperature of a medium such as hot or cold water or oil circulated through piping embedded inside the mold; etc.
• the norbornene-based resin can be obtained, for example, by opening the mold and demolding.
• Example 1 (Preparation of catalyst solution) A catalyst solution was prepared by dissolving 2 parts of a ruthenium carbene complex represented by the following formula (6) (benzylidene(1,3-dimesitylimidazolidin-2-ylidene)(tricyclohexylphosphine)ruthenium dichloride, C848) and 100 parts of triphenylphosphine (TPP) in 100 parts of cyclopentanone as a metathesis polymerization catalyst. The prepared catalyst solution was stored for one month under a nitrogen atmosphere at 25°C. The amount of triphenylphosphine in the obtained catalyst solution, calculated as phosphorus atoms, relative to 1 mole of ruthenium in the ruthenium carbene complex represented by the following formula (6) was 162 moles.
• a ruthenium carbene complex represented by the following formula (6) benzylidene(1,3-dimesitylimidazolidin-2-ylidene)(tricyclohexyl
• TPP triphenylphosphine
• RIM monomer manufactured by Zeon Corporation
• the total amount of the obtained monomer liquid and the total amount of the catalyst liquid stored for one month were mixed in a container equipped with a thermometer having a thermocouple to prepare a polymerizable composition, and the curing time of the polymerizable composition was measured.
• the curing time was measured under the condition of an initial temperature of 30°C, and the time when the measured temperature reached 100°C due to heat caused by polymerization was regarded as the curing time. The results are shown in Table 1.
• the composition of the RIM monomer was about 90 parts of dicyclopentadiene and about 10 parts of tricyclopentadiene (about 90% dicyclopentadiene and about 10% tricyclopentadiene).
• the amount of triphenylphosphine in terms of phosphorus atoms relative to 1 mole of ruthenium in the ruthenium carbene complex represented by the above formula (6) in the obtained polymerizable composition was 324 moles.
• Example 2 The catalyst solution obtained in the same manner as in Example 1 was stored for one month under the same conditions as in Example 1.
• a monomer solution was obtained in the same manner as in Example 1, except that the amount of triphenylphosphine (TPP) was changed to 150 parts.
• TPP triphenylphosphine
• the entire amount of the obtained monomer solution and the entire amount of the catalyst solution stored for one month were mixed to obtain a polymerizable composition, and the curing time of the polymerizable composition was measured in the same manner as in Example 1.
• Table 1 In the obtained polymerizable composition, the amount of triphenylphosphine, calculated as phosphorus atoms, per 1 mole of ruthenium in the ruthenium carbene complex represented by the above formula (6) was 405 moles.
• Example 3 The catalyst solution obtained in the same manner as in Example 1 was stored for one month under the same conditions as in Example 1.
• a monomer solution was obtained in the same manner as in Example 1, except that the amount of triphenylphosphine (TPP) was changed to 200 parts.
• TPP triphenylphosphine
• the entire amount of the obtained monomer solution and the entire amount of the catalyst solution stored for one month were mixed to obtain a polymerizable composition, and the curing time of the polymerizable composition was measured in the same manner as in Example 1.
• Table 1 In the obtained polymerizable composition, the amount of triphenylphosphine, calculated as phosphorus atoms, per 1 mole of ruthenium in the ruthenium carbene complex represented by the above formula (6) was 485 moles.
• Example 1 The catalyst liquid obtained in the same manner as in Example 1 was stored for one month under the same conditions as in Example 1. A monomer liquid was obtained in the same manner as in Example 1, except that triphenylphosphine (TPP) was not added. Then, the entire amount of the obtained monomer liquid and the entire amount of the catalyst liquid stored for one month were mixed to prepare a polymerizable composition, and the curing time of the polymerizable composition was measured in the same manner as in Example 1. The results are shown in Table 1. In the obtained polymerizable composition, the amount of triphenylphosphine, calculated as phosphorus atoms, per 1 mole of ruthenium in the ruthenium carbene complex represented by the above formula (6) was 162 moles.
• TPP triphenylphosphine
• Catalyst (C848) is benzylidene(1,3-dimesitylimidazolidin-2-ylidene)(tricyclohexylphosphine)ruthenium dichloride;
• TPP is triphenylphosphine.
• the obtained polymerizable composition had a sufficiently long curing time of 400 seconds or more, and the curing reaction also occurred sufficiently, thereby realizing excellent workability (Examples 1 to 3).
• TPP triphenylphosphine
• TPP triphenylphosphine
• Example 4 (Preparation of catalyst solution) A catalyst solution was prepared by dissolving 2 parts of a ruthenium carbene complex represented by the following formula (7) ((1,3-dimesitylimidazolidin-2-ylidene)(3-methyl-2-buten-1-ylidene)(tricyclopentylphosphine)ruthenium dichloride, C827) as a metathesis polymerization catalyst and 100 parts of triphenylphosphine (TPP) in 100 parts of cyclopentanone.
• TPP triphenylphosphine
• the prepared catalyst solution was stored for 6 months under a nitrogen atmosphere at 25°C.
• the amount of triphenylphosphine in the obtained catalyst solution, calculated as phosphorus atoms, relative to 1 mole of ruthenium in the ruthenium carbene complex represented by the following formula (7) was 158 moles.
• TPP triphenylphosphine
• the composition of the RIM monomer was about 90 parts of dicyclopentadiene and about 10 parts of tricyclopentadiene (about 90% dicyclopentadiene and about 10% tricyclopentadiene).
• the amount of triphenylphosphine in terms of phosphorus atoms relative to 1 mole of ruthenium in the ruthenium carbene complex represented by the above formula (6) in the obtained polymerizable composition was 473 moles.
• a mold made of aluminum 5052 with release treatment and inner dimensions of 300 mm in length, 250 mm in width, and 4 mm in depth was prepared, and covered with a flat plate made of aluminum 5052.
• the mold was set to 25°C, and the remaining part of the monomer liquid obtained above and the remaining part of the catalyst liquid stored for 6 months above were mixed and introduced into the mold to fill it up.
• the mold was subsequently heated to 120°C and left for 1 hour.
• the mold was cooled to room temperature and then demolded to obtain a norbornene-based resin.
• the norbornene-based resin thus obtained was subjected to measurements of bending strength, bending modulus, HDT (edgewise) and heat loss according to the methods described below.
• the results are shown in Table 2.
• Bending strength and bending modulus of elasticity were measured in accordance with ISO178 using a universal testing machine AG5000 (manufactured by Shimadzu Corporation).
• ⁇ HDT (edgewise) HDT (edgewise) was measured using a HDT measuring device manufactured by Toyo Seiki Co., Ltd. in accordance with ISO 75-2.
• Weight loss on heating TG/DTA measurement was carried out using a TG/DTA6200 (manufactured by Hitachi High-Tech Science Corporation) at a heating rate of 20° C./min, and the weight loss up to 150° C. was measured based on 30° C.
• Example 5 The catalyst solution obtained in the same manner as in Example 4 was stored for 6 months under the same conditions as in Example 4.
• a monomer solution was obtained in the same manner as in Example 4, except that 50 parts of trimethoxyphenylphosphine (TMPP) was mixed instead of 200 parts of triphenylphosphine (TPP). Then, the total amount of the obtained monomer solution and the total amount of the catalyst solution stored for 6 months were mixed to obtain a polymerizable composition, and the curing time of the polymerizable composition was measured in the same manner as in Example 4. The results are shown in Table 2.
• TMPP trimethoxyphenylphosphine
• TPP triphenylphosphine
• the total amount of triphenylphosphine and trimethoxyphenylphosphine, calculated as phosphorus atoms, per 1 mole of ruthenium in the ruthenium carbene complex represented by the above formula (7) was 217 moles.
• Example 6 The catalyst solution obtained in the same manner as in Example 4 was stored for 6 months under the same conditions as in Example 4.
• a monomer solution was obtained in the same manner as in Example 4, except that 100 parts of trimethoxyphenylphosphine (TMPP) was mixed instead of 200 parts of triphenylphosphine (TPP). Then, the total amount of the obtained monomer solution and the total amount of the catalyst solution stored for 6 months were mixed to obtain a polymerizable composition, and the curing time of the polymerizable composition was measured in the same manner as in Example 4. The results are shown in Table 2.
• TMPP trimethoxyphenylphosphine
• TPP triphenylphosphine
• the total amount of triphenylphosphine and trimethoxyphenylphosphine, calculated as phosphorus atoms, per 1 mole of ruthenium in the ruthenium carbene complex represented by the above formula (7) was 275 moles.
• Example 7 The catalyst solution obtained in the same manner as in Example 4 was stored for 6 months under the same conditions as in Example 4.
• a monomer solution was obtained in the same manner as in Example 4, except that 150 parts of trimethoxyphenylphosphine (TMPP) was mixed instead of 200 parts of triphenylphosphine (TPP). Then, the total amount of the obtained monomer solution and the total amount of the catalyst solution stored for 6 months were mixed to obtain a polymerizable composition, and the curing time of the polymerizable composition was measured in the same manner as in Example 4. The results are shown in Table 2.
• TMPP trimethoxyphenylphosphine
• TPP triphenylphosphine
• the total amount of triphenylphosphine and trimethoxyphenylphosphine, calculated as phosphorus atoms, per 1 mole of ruthenium in the ruthenium carbene complex represented by the above formula (7) was 334 moles.
• Example 8 The catalyst solution obtained in the same manner as in Example 4 was stored for 6 months under the same conditions as in Example 4.
• a monomer solution was obtained in the same manner as in Example 4, except that 200 parts of trimethoxyphenylphosphine (TMPP) was used instead of 200 parts of triphenylphosphine (TPP).
• TMPP trimethoxyphenylphosphine
• TPP triphenylphosphine
• the total amount of triphenylphosphine and trimethoxyphenylphosphine, calculated as phosphorus atoms, per 1 mole of ruthenium in the ruthenium carbene complex represented by the above formula (7) was 393 moles.
• Example 9 The catalyst solution obtained in the same manner as in Example 4 was stored for 6 months under the same conditions as in Example 4.
• a monomer solution was obtained in the same manner as in Example 4, except that 50 parts of trimethoxyphenylphosphine (TMPP) was further blended together with 200 parts of triphenylphosphine (TPP). Then, the total amount of the obtained monomer solution and the total amount of the catalyst solution stored for 6 months were mixed to obtain a polymerizable composition, and the curing time of the polymerizable composition was measured in the same manner as in Example 4. The results are shown in Table 2.
• the total amount of triphenylphosphine and trimethoxyphenylphosphine, calculated as phosphorus atoms, per 1 mole of ruthenium in the ruthenium carbene complex represented by the above formula (7) was 532 moles.
• Example 10 The catalyst liquid obtained in the same manner as in Example 4 was stored for 6 months under the same conditions as in Example 4.
• a monomer liquid was obtained in the same manner as in Example 4, except that 100 parts of trimethoxyphenylphosphine (TMPP) was further blended together with 200 parts of triphenylphosphine (TPP). Then, half of the total amount of the obtained monomer liquid and half of the total amount of the catalyst liquid stored for 6 months were mixed to obtain a polymerizable composition, and the curing time of the polymerizable composition was measured in the same manner as in Example 4.
• TMPP trimethoxyphenylphosphine
• TPP triphenylphosphine
• a norbornene-based resin was obtained in the same manner as in Example 4 using the remaining part of the obtained monomer liquid and the remaining part of the catalyst liquid stored for 6 months, and was evaluated in the same manner.
• the results are shown in Table 2.
• the total amount of triphenylphosphine and trimethoxyphenylphosphine, calculated as phosphorus atoms, per 1 mole of ruthenium in the ruthenium carbene complex represented by the above formula (7) was 591 moles.
• Example 11 The catalyst solution obtained in the same manner as in Example 4 was stored for 6 months under the same conditions as in Example 4.
• a monomer solution was obtained in the same manner as in Example 4, except that 200 parts of 1,4-bis(diphenylphosphinobutane) (DPPB) was blended instead of 200 parts of triphenylphosphine (TPP).
• DPPB 1,4-bis(diphenylphosphinobutane)
• TPP triphenylphosphine
• a polymerizable composition was prepared by mixing half of the total amount of the obtained monomer solution with half of the total amount of the catalyst solution stored for 6 months, and the curing time of the polymerizable composition was measured in the same manner as in Example 4.
• a norbornene-based resin was obtained in the same manner as in Example 4 using the remaining part of the obtained monomer solution and the remaining part of the catalyst solution stored for 6 months, and was evaluated in the same manner.
• the results are shown in Table 2.
• the total amount of triphenylphosphine and 1,4-bis(diphenylphosphinobutane) calculated as phosphorus atoms relative to 1 mole of ruthenium in the ruthenium carbene complex represented by the above formula (7) was 546 moles (the total of 168 moles of triphenylphosphine and 433 moles of 1,4-bis(diphenylphosphinobutane)).
• Example 2 The catalyst liquid obtained in the same manner as in Example 4 was stored for 6 months under the same conditions as in Example 4.
• a monomer liquid was obtained in the same manner as in Example 4, except that triphenylphosphine (TPP) was not added.
• a polymerizable composition was prepared by mixing half of the total amount of the obtained monomer liquid with half of the total amount of the catalyst liquid stored for 6 months, and the curing time of the polymerizable composition was measured in the same manner as in Example 4.
• a norbornene-based resin was obtained using the remaining part of the obtained monomer liquid and the remaining part of the catalyst liquid stored for 6 months in the same manner as in Example 4, and was evaluated in the same manner. The results are shown in Table 2.
• the amount of triphenylphosphine, calculated as phosphorus atoms, per 1 mole of ruthenium in the ruthenium carbene complex represented by the above formula (7) was 158 moles.
• Catalyst (C827) is (1,3-dimesitylimidazolidin-2-ylidene)(3-methyl-2-buten-1-ylidene)(tricyclopentylphosphine)ruthenium dichloride;
• TPP is triphenylphosphine;
• TMPP trimethoxyphenylphosphine.
• the obtained polymerizable composition had a sufficiently long curing time of 400 seconds or more, and the curing reaction also occurred sufficiently, thereby realizing excellent workability (Examples 4 to 11).
• TPP triphenylphosphine

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