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
• • 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
• • 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 catalyst liquid that has excellent storage stability and exhibits excellent catalytic activity even after long-term storage, and to a polymerizable composition obtained using such a catalyst liquid.
• 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 applications.
• 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.
• Patent Document 1 While the ruthenium carbene complex disclosed in Patent Document 1 is generally used in the form of a catalyst liquid by dissolving or dispersing it in a solvent, there is an issue that storage stability is insufficient when stored in the form of a catalyst liquid.
• the present invention aims to provide a catalyst liquid that has excellent storage stability and exhibits excellent catalytic activity even after long-term storage.
• the inventors conducted research to achieve the above-mentioned object, and discovered that by blending a specific amount of a phosphorus-atom-containing coordinating compound in a catalyst solution containing a ruthenium carbene complex having phosphines as ligands as a metathesis polymerization catalyst, the catalyst solution can be made to have excellent storage stability and exhibit excellent catalytic activity even after long-term storage, leading to the completion of the present invention.
• a catalyst solution comprising a metathesis polymerization catalyst, a coordination compound containing a phosphorus atom, and a solvent
• the metathesis polymerization catalyst is a ruthenium carbene complex represented by the following general formula (1) or (2):
• the catalyst solution has a phosphorus atom-containing coordination compound content of 6 to 1,000 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.
• 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 may have a substituent.
• the present invention provides a catalyst liquid that has excellent storage stability and exhibits excellent catalytic activity even after long-term storage, and a polymerizable composition obtained using such a catalyst liquid.
• the catalyst solution of the present invention is a catalyst solution containing a metathesis polymerization catalyst, a coordination compound containing a phosphorus atom, and a solvent
• 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 coordinating compound in the catalyst solution is 6 to 1,000 moles, calculated as phosphorus atoms, per mole of ruthenium atoms in the metathesis polymerization catalyst.
• 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.
• R 5 , R 6 , R 7 and R 8 in the above general formula (3) and R 5 and R 6 in the above general formula (4) are hydrogen atoms.
• R 3 and R 4 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 catalyst solution of the present invention contains a coordination compound containing a phosphorus atom, and the content of the coordination compound containing a phosphorus atom is 6 to 1000 moles of phosphorus atoms per mole of ruthenium atoms in the metathesis polymerization catalyst.
• the coordination compound containing a phosphorus atom in the catalyst solution in the above-mentioned specific amount, it is possible to make the catalyst solution have excellent storage stability even when the metathesis polymerization catalyst is dissolved or dispersed in a solvent to prepare a catalyst solution, and as a result, it is possible to exhibit excellent catalytic activity even after long-term storage.
• 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, but are preferably the same group.
• 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, and triethoxyphenylphosphine.
• the compound represented by the above general formula (5) may be used alone or in combination of two or more. Among these, triphenylphosphine and trimethoxyphenylphosphine are preferred, and it is also 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 catalyst solution of the present invention is 6 to 1000 moles, preferably 10 to 850 moles, more preferably 20 to 700 moles, even more preferably 40 to 500 moles, and particularly preferably 120 to 200 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 catalyst solution of the present invention, calculated as weight, is preferably 2 to 320 parts by mass, more preferably 3 to 270 parts by mass, even more preferably 6 to 220 parts by mass, even more preferably 15 to 160 parts by mass, and particularly preferably 35 to 65 parts by mass, per part by mass of the metathesis polymerization catalyst.
• the storage stability of the catalyst solution will decrease, while if the content of the phosphorus atom-containing coordination compound is too high, the catalytic activity will be insufficient when a norbornene-based monomer is blended as a polymerizable monomer to form a polymerizable composition, and the polymerization reaction may not proceed sufficiently.
• the catalyst solution of the present invention contains a solvent in addition to the metathesis polymerization catalyst and the phosphorus-containing coordinating compound.
• the solvent is not particularly limited as long as it is inert to the metathesis polymerization catalyst and the phosphorus-containing coordinating compound, but examples of the solvent 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. Among these, ketones are preferred, and cyclopentanone is more preferred.
• the solvent may be used alone or in combination of two or more.
• the amount of the solvent in the catalyst solution of the present invention is not particularly limited and may be adjusted appropriately depending on the viscosity of the catalyst solution, etc., but is preferably 10 to 1,000 parts by mass, more preferably 20 to 800 parts by mass, and even more preferably 30 to 500 parts by mass, per part by mass of the metathesis polymerization catalyst.
• the method for preparing the catalyst solution of the present invention is not particularly limited, but it may be prepared by mixing a metathesis polymerization catalyst, a coordination compound containing a phosphorus atom, and a solvent.
• the polymerizable composition of the present invention is prepared by blending the above-mentioned catalyst liquid of the present invention with a norbornene-based monomer as a polymerizable monomer.
• the norbornene-based monomer may be any compound having a norbornene ring structure, and is not particularly limited.
• 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”).
• 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%, more preferably 80 to 99.5 mass%, even more preferably 85 to 99 mass%, and particularly preferably 87 to 98 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 content of the metathesis polymerization catalyst in the polymerizable composition of the present invention 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 including cyclic olefin monomers.
• the content of the metathesis polymerization catalyst in the polymerizable composition of the present invention 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 including cyclic olefin monomers.
• a coordination compound containing a phosphorus atom may be added to the polymerizable composition of the present invention in addition to the coordination compound containing a phosphorus atom contained in the catalyst solution of the present invention.
• the coordination compound containing a phosphorus atom to be added may be the same as the coordination compound containing a phosphorus atom contained in the catalyst solution of the present invention or a coordination compound having multiple phosphorus atoms, and may be used alone or in combination of two or more.
• the coordination compound containing a phosphorus atom to be added may be the same compound as the coordination compound containing a phosphorus atom contained in the catalyst solution of the present invention, or it may be a different compound.
• the amount of the coordinating compound containing a phosphorus atom to be added is not particularly limited and may be determined according to the polymerization reaction time (curing time); however, the total amount of the coordinating compound containing a phosphorus atom contained in the polymerizable composition of the present invention (i.e., the total amount of the coordinating compound containing a phosphorus atom contained in the catalyst solution of the present invention and the additionally added coordinating compound containing a phosphorus atom) is preferably 6 to 2,000 moles, more preferably 10 to 1,700 moles, even more preferably 20 to 1,400 moles, even more preferably 40 to 1,000 moles, and particularly preferably 120 to 400 moles, in terms of phosphorus atoms, per mole of ruthenium atoms in the metathesis polymerization catalyst contained in the polymerizable composition.
• the content of the phosphorus-atom-containing coordinating compound in the polymerizable composition of the present invention is the total amount of the phosphorus-atom-containing coordinating compound (i.e., the total amount of the phosphorus-atom-containing coordinating compound contained in the catalyst solution of the present invention and the additional phosphorus-atom-containing coordinating compound added), preferably 2 to 630 parts by mass, more preferably 3 to 540 parts by mass, even more preferably 6 to 450 parts by mass, even more preferably 15 to 350 parts by mass, and particularly preferably 35 to 150 parts by mass, per part by mass of the metathesis polymerization catalyst.
• 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 dibenzidine.
• MDI 4,4'-methylene diphenyl diisocyanate
• toluene-2,4-diisocyanate 4-methoxy-1
• 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 various fillers can be used, and although there is no particular limitation, 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 with the above-mentioned catalyst liquid of the present invention according to a known method.
• the polymerizable composition of the present invention may be prepared by preparing the above-mentioned catalyst liquid of the present invention and one or more other premixed liquids such as a monomer liquid, and mixing the catalyst liquid and the other premixed liquid such as a monomer liquid using a mixing device or the like immediately before making into a norbornene-based resin.
• the catalyst liquid and the other premixed liquid such as a monomer liquid will not undergo bulk polymerization when used alone, but are prepared so that when all the liquids are mixed together, a polymerizable composition containing each component in a predetermined ratio (the total content of each component is 100% by mass).
• Optional components such as radical generators, diisocyanate compounds, and polyfunctional (meth)acrylate compounds may be contained in either the catalyst liquid or other premixed liquids such as the monomer liquid, or may be added in the form of a mixed liquid separate from these.
• mixing devices used to mix the catalyst liquid with other premixed liquids such as monomer liquid include impingement mixers commonly used in reaction injection molding, as well as low-pressure mixers such as dynamic mixers and static mixers.
• the norbornene-based resin of the present invention is obtained by bulk polymerization of the above-mentioned polymerizable composition of the present invention.
• Methods for producing the norbornene-based resin of the present invention include, for example, directly mixing the above-mentioned catalyst liquid with other premixed liquids such as monomer liquid, or using a mixing device equipped with a mixer or an impingement mixer in which each liquid is introduced into a separate mixing head and mixed instantaneously, and bulk polymerization is performed in a mold or on a substrate.
• the molding die is not particularly limited, but for example, a die formed of a male die and a female die can be used.
• the die used does not necessarily have to be a highly rigid and expensive die, and is not limited to a metal die, but a resin die or a simple formwork can be used.
• a metal die the material is not particularly limited, but examples include steel, aluminum, zinc alloy, nickel, copper, chromium, etc., and the die may be manufactured by any method such as casting, forging, thermal spraying, electroforming, etc., or may be plated.
• the structure of the die may be determined taking into consideration the pressure when the polymerizable composition is injected into the die.
• the clamping pressure of the die 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 amount of triphenylphosphine in the obtained catalyst solution, calculated as phosphorus atoms, per 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)(tricyclohexylphosphine)ruthenium dichloride, C848
• TPP triphen
• Catalyst solution storage test The catalyst solution prepared above was stored under a nitrogen atmosphere at 25° C. for one month.
• Example 2 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 100 parts of triphenylphosphine (TPP) was further added.
• TPP triphenylphosphine
• the entire amount of the obtained monomer liquid and the entire amount of the catalyst liquid 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. The results are shown in Table 1.
• the amount of triphenylphosphine calculated as phosphorus atoms relative to 1 mole of ruthenium in the ruthenium carbene complex represented by the above formula (6) was 324 moles (the total of 162 moles added to the catalyst solution and 162 moles added during the preparation of the polymerizable composition).
• Example 1 A catalyst solution was obtained in the same manner as in Example 1, except that triphenylphosphine (TPP) was not added, and the obtained catalyst solution was stored for one month under the same conditions as in Example 1. A monomer solution was also prepared in the same manner as in Example 1. Then, the entire amount of the obtained monomer solution and the entire amount of the catalyst solution 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.
• TPP triphenylphosphine
• Catalyst (C848) is benzylidene(1,3-dimesitylimidazolidin-2-ylidene)(tricyclohexylphosphine)ruthenium dichloride;
• TPP is triphenylphosphine.
• Example 3 (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) and 100 parts of triphenylphosphine (TPP) in 100 parts of cyclopentanone as a metathesis polymerization catalyst.
• TPP triphenylphosphine
• the amount of triphenylphosphine in the obtained catalyst solution, calculated as phosphorus atoms, per mole of ruthenium in the ruthenium carbene complex represented by the following formula (7) was 158 moles.
• Catalyst solution storage test The catalyst solution prepared above was stored under a nitrogen atmosphere at 25° C. for six months.
• 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 cooled to 10°C and further left for 1 hour, so that the polymerizable composition did not flow in the mold.
• the mold was then heated to 120°C and left for 1 hour.
• the mold was cooled to room temperature and 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 4 The catalyst solution obtained in the same manner as in Example 3 was stored for 6 months under the same conditions as in Example 3.
• a monomer solution was obtained in the same manner as in Example 3, except that 200 parts of triphenylphosphine (TPP) was further blended.
• 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 3.
• a norbornene-based resin was obtained using the remaining part of the obtained monomer solution and the remaining part of the catalyst solution stored for 6 months in the same manner as in Example 3, and was evaluated in the same manner. The results are shown in Table 2.
• the amount of triphenylphosphine calculated as phosphorus atoms relative to 1 mole of ruthenium in the ruthenium carbene complex represented by the above formula (7) was 474 moles (the total of 162 moles added to the catalyst solution and 324 moles added during the preparation of the polymerizable composition).
• Example 5 The catalyst solution obtained in the same manner as in Example 3 was stored for 6 months under the same conditions as in Example 3.
• a monomer solution was obtained in the same manner as in Example 3, except that 200 parts of triphenylphosphine (TPP) and 100 parts of trimethoxyphenylphosphine (TMPP) were further blended. Then, half of the total amount of the obtained monomer solution and half of 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 3.
• TPP triphenylphosphine
• TMPP trimethoxyphenylphosphine
• a norbornene-based resin was obtained in the same manner as in Example 3 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 trimethoxyphenylphosphine, calculated as phosphorus atoms, relative to 1 mole of ruthenium in the ruthenium carbene complex represented by the above formula (7) was 591 moles (the total of 158 moles added to the catalyst solution and 433 moles added during the preparation of the polymerizable composition).
• Example 6 A catalyst solution was prepared by dissolving 1 part of a ruthenium carbene complex represented by the above formula (7) ((1,3-dimesitylimidazolidin-2-ylidene)(3-methyl-2-buten-1-ylidene)(tricyclopentylphosphine)ruthenium dichloride, C827) and 20 parts of trimethoxyphenylphosphine (TMPP) in 90 parts of cyclopentanone as a metathesis polymerization catalyst.
• TMPP trimethoxyphenylphosphine
• the catalyst solution prepared above was then stored for 6 months under a nitrogen atmosphere at 25°C. Then, the entire amount of the monomer liquid prepared in the same manner as in Example 3 was mixed with the entire amount of the catalyst liquid stored for 6 months to prepare a polymerizable composition, and the curing time of the polymerizable composition was measured in the same manner as in Example 3. The results are shown in Table 1. In the obtained polymerizable composition, the amount of trimethoxyphenylphosphine, calculated as phosphorus atoms, relative to 1 mole of ruthenium in the ruthenium carbene complex represented by the above formula (7) was 47 moles.
• Example 7 A catalyst solution was prepared by dissolving 2 parts of a ruthenium carbene complex represented by the above formula (7) ((1,3-dimesitylimidazolidin-2-ylidene)(3-methyl-2-buten-1-ylidene)(tricyclopentylphosphine)ruthenium dichloride, C827) and 40 parts of trimethoxyphenylphosphine (TMPP) in 180 parts of cyclopentanone as a metathesis polymerization catalyst.
• TMPP trimethoxyphenylphosphine
• the catalyst solution prepared above was then stored for 6 months under a nitrogen atmosphere at 25°C. Then, the entire amount of the monomer liquid prepared in the same manner as in Example 3 was mixed with the entire amount of the catalyst liquid stored for 6 months to prepare a polymerizable composition, and the curing time of the polymerizable composition was measured in the same manner as in Example 3. The results are shown in Table 1. In the obtained polymerizable composition, the amount of trimethoxyphenylphosphine, calculated as phosphorus atoms, relative to 1 mole of ruthenium in the ruthenium carbene complex represented by the above formula (7) was 47 moles.
• Example 2 A catalyst solution was obtained in the same manner as in Example 3, except that triphenylphosphine (TPP) was not added, and the obtained catalyst solution was stored for 6 months under the same conditions as in Example 3. A monomer solution was also prepared in the same manner as in Example 3. Then, the entire amount of the obtained monomer solution and the entire amount of the catalyst solution stored for 6 months were mixed to prepare a polymerizable composition, and the curing time of the polymerizable composition was measured in the same manner as in Example 3. The results are shown in Table 2.
• TPP triphenylphosphine
• Catalyst (C827) is (1,3-dimesitylimidazolidin-2-ylidene)(3-methyl-2-buten-1-ylidene)(tricyclopentylphosphine)ruthenium dichloride;
• TPP is triphenylphosphine;
• TMPP trimethoxyphenylphosphine.

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