Polymerizable composition and norbornene resin

Abstract

Provided is a polymerizable composition containing a norbornene-based monomer, a metathesis polymerization catalyst, and a phosphorus atom-containing coordination compound, the metathesis polymerization catalyst being a ruthenium carbene complex represented by general formula (1) or general formula (2), and the amount of the ruthenium carbene complex being 1 mol / mol of ruthenium atoms per 1 mol / mol of the metathesis polymerization catalyst, and the amount of the phosphorus atom per 1 mol / mol of ruthenium atoms per 1 mol / mol of the metathesis polymerization catalyst. The content of the coordination compound containing phosphorus atoms is 170-2000 moles in terms of phosphorus atoms. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a polymerizable composition in which the curing time is controlled within an appropriate range and excellent workability is achieved, and a norbornene-based resin obtained using the polymerizable composition. Background Art

[0002] Norbornene-based resins obtained by ring-opening polymerization of norbornene-based monomers are known to be excellent in mechanical strength, heat resistance, low hygroscopicity, dielectric properties, and the like, and are used in various applications.

[0003] For example, Patent Document 1 discloses a ruthenium carbene complex having a phosphine as a ligand as a metathesis polymerization catalyst for ring-opening polymerization of a norbornene-based monomer. Patent Document 1 also discloses a polymerizable composition using such a ruthenium carbene complex.

[0004] However, the polymerizable composition using a ruthenium carbene complex as a polymerization catalyst disclosed in Patent Document 1 has problems such as short curing time and poor workability when filling into a mold.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2001-139668. Summary of the invention

[0008] Problem that the invention aims to solve

[0009] An object of the present invention is to provide a polymerizable composition in which the curing time is controlled within an appropriate range and excellent workability can be achieved.

[0010] Solutions for solving problems

[0011] The present inventors have conducted research to achieve the above-mentioned purpose and have found that by adding a specific amount of a coordination compound containing a phosphorus atom to a polymerizable composition containing a norbornene-based monomer and a ruthenium carbene complex having a phosphine as a specific ligand as a metathesis polymerization catalyst, the curing time of the polymerizable composition can be controlled within an appropriate range and excellent operability can be achieved, thereby completing the present invention.

[0012] That is, according to the present invention, the following inventions are provided.

[0013] [1] A polymerizable composition comprising a norbornene-based monomer, a metathesis polymerization catalyst, and a coordination compound containing a phosphorus atom,

[0014] The metathesis polymerization catalyst is a ruthenium carbene complex represented by the following general formula (1) or (2):

[0015] The content of the complex containing phosphorus atoms is 170 to 2000 mol in terms of phosphorus atoms per 1 mol of ruthenium atoms in the metathesis polymerization catalyst.

[0016] [Chemical formula 1]

[0017]

[0018] (In the above general formulas (1) and (2), R 1 and R 2 Each is 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. 1 and X 2 Each independently represents any anionic ligand. 1 and L 2 is a carbene compound or phosphine containing a heteroatom, L 1 and L 2 At least one of them is a phosphine.)

[0019] [2] The polymerizable composition according to [1], wherein the L 1 is a compound represented by the following general formula (3) or (4), wherein L 2 It is a phosphine.

[0020] [Chemical formula 2]

[0021]

[0022] (In the above general formulas (3) and (4), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each is 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.

[0023] [3] The polymerizable composition according to [1] or [2], wherein the phosphine is a trialkylphosphine which may have a substituent.

[0024] [4] The polymerizable composition according to any one of [1] to [3], wherein the coordination compound containing a phosphorus atom is a compound represented by the following general formula (5).

[0025] [Chemical formula 3]

[0026]

[0027] (In the above general formula (5), R 9 ~R 11 Each is independently an alkyl group which may have a substituent, an aryl group which may have a substituent, or a polyvalent phosphine formed via an alkylene group.)

[0028] [5] The polymerizable composition according to any one of [1] to [4], wherein

[0029] The polymerizable composition is formed from two or more pre-formulated solutions that do not undergo polymerization reaction independently, and the polymerizable composition can be formed by mixing the pre-formulated solutions.

[0030] [6] A norbornene-based resin obtained by bulk polymerization of the polymerizable composition according to any one of [1] to [5].

[0031] Effects of the Invention

[0032] According to the present invention, it is possible to provide a polymerizable composition in which the curing time is controlled within an appropriate range and excellent workability is achieved, and a norbornene-based resin obtained using the polymerizable composition. DETAILED DESCRIPTION

[0033] <Polymerizable Composition>

[0034] The polymerizable composition of the present invention comprises a norbornene-based monomer, a metathesis polymerization catalyst, and a coordination compound containing a phosphorus atom.

[0035] The metathesis polymerization catalyst is a ruthenium carbene complex represented by the general formula (1) or (2) described below.

[0036] The content of the complex containing phosphorus atoms is 170 to 2000 mol in terms of phosphorus atoms per 1 mol of ruthenium atoms in the metathesis polymerization catalyst.

[0037] As the norbornene monomer, there is no particular limitation as long as it is a compound having a norbornene ring structure, and examples thereof include bicyclic compounds such as norbornene and norbornadiene; tricyclic compounds such as dicyclopentadiene; tetracyclic compounds such as tetracyclododecene; pentacyclic compounds such as tricyclopentadiene; heptacyclic compounds such as tetracyclopentadiene; and derivatives thereof having an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, an epoxy group, or a (meth)acrylyl group [CH2=CHCH2- and / or CH2=C(CH3)CH2-]. In addition, in the present specification, "(meth)acrylyl group" refers to an acryloyl group and / or a methacryloyl group (hereinafter, the same applies to "(meth)acryloyl group" etc.). The norbornene monomer can be used alone or in combination of two or more. As the norbornene monomer, the above tricyclic compounds are preferred, and dicyclopentadiene is particularly preferred, from the viewpoint of further improving the effects of the present invention. The norbornene monomer used preferably contains 50% by mass or more of the above tricyclic compounds, especially dicyclopentadiene.

[0038] The content of the norbornene-based monomer in the polymerizable composition of the present invention is not particularly limited, and is preferably 80 to 100 mass %, preferably 80 to 95 mass %, more preferably 85 to 92 mass %, and further preferably 87 to 90 mass %, based on 100 mass % of the total polymerizable monomer contained in the polymerizable composition. By making the content of the norbornene-based monomer within the above range, the strength of the obtained norbornene-based resin can be further improved.

[0039] Furthermore, in the present invention, as the polymerizable monomer contained in the polymerizable composition, a monocyclic cycloolefin may also be used.

[0040] The monocyclic cycloolefin is not particularly limited, and examples thereof include 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 alkylene group having 1 to 10 carbon atoms, an epoxy group, or a (meth)acryloyl group. The monocyclic cycloolefin can be used alone or in combination of two or more.

[0041] In addition, the polymerizable composition of the present invention may contain other polymerizable monomers that can polymerize with norbornene-based monomers and monocyclic cycloolefins used as needed. Examples of such other polymerizable monomers include other cycloolefin monomers, (meth)acrylate monomers such as phenoxyethylene glycol (meth)acrylate, and the like.

[0042] The content of the polymerizable monomer other than the norbornene-based monomer 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, further preferably 30% by mass or less, and may be 0% by mass, based on 100% by mass of the total polymerizable monomer contained in the polymerizable composition.

[0043] In addition, in the polymerizable composition of the present invention, the lower limit of the content of the total polymerizable monomer can be preferably 10 mass% or more, more preferably 15 mass% or more, further preferably 20 mass% or more, further preferably 50 mass% or more, and particularly preferably 80 mass% or more, and the upper limit of the content of the total polymerizable monomer can be preferably 99.5 mass% or less, more preferably 99 mass% or less, further preferably 95 mass% or less, further preferably 93 mass% or less, and particularly preferably 90 mass% or less, based on 100 mass% of the total polymerizable composition.

[0044] The metathesis polymerization catalyst used in the present invention is a ruthenium carbene complex represented by the following general formula (1) or (2).

[0045] [Chemical formula 4]

[0046]

[0047] In the above general formulas (1) and (2), R 1 and R 2 Each is 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. 1 and R 2 Examples of groups that are bonded to each other to form a ring include indenyl groups that may have a substituent, such as phenylindenyl group.

[0048] 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 include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, and a The organic groups having 1 to 20 carbon atoms may include an alkyl group having 1 to 10 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, a carbonyloxy group, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, an alkylsulfinyl group having 1 to 20 carbon atoms, an alkylsulfonic acid group having 1 to 20 carbon atoms, an arylsulfonic acid group having 6 to 20 carbon atoms, a phosphonic acid group, an arylphosphonic acid group having 6 to 20 carbon atoms, an alkylammonium group having 1 to 20 carbon atoms, and an arylammonium group having 6 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 also have a substituent. Examples of the substituent 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.

[0049] X 1 and X 2 Each independently represents an arbitrary anionic ligand. The anionic ligand is a ligand that has a negative charge when separated from the central metal atom, and examples thereof include a halogen atom, a diketonate group, a substituted cyclopentadienyl group, an alkoxy group, an aryloxy group, and a carboxyl group.

[0050] L 1 and L 2 is a carbene compound or phosphine containing a heteroatom, L 1 and L 2 At least one of them is a phosphine.

[0051] The heteroatom-containing carbene compound is preferably a compound represented by the following general formula (3) or (4), and is more preferably a compound represented by the following general formula (3) from the viewpoint of improving the catalytic activity.

[0052] [Chemical formula 5]

[0053]

[0054] In the above general formulas (3) and (4), R 3 , R 4 , R 5 , R 6 , R 7 and R 8Each independently represents 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-mentioned general formulae (1) and (2).

[0055] In addition, R 3 , R 4 , R 5 , R 6 , R 7 and R 8 They may be bonded to each other in any combination to form a ring.

[0056] In order to further enhance the effect of the present invention, it is preferred that R 5 , R 6 , R 7 and R 8 , R of the above general formula (4) 5 and R 6 is a hydrogen atom. In addition, R 3 and R 4 An aryl group which may have a substituent is preferred, a phenyl group having an alkyl group having 1 to 10 carbon atoms as a substituent is more preferred, and a mesityl group is further preferred.

[0057] The phosphine is not particularly limited, and from the viewpoint of catalytic activity, examples include trialkylphosphines that may have a substituent or triarylphosphines that may have a substituent, etc., preferably trialkylphosphines that may have a substituent, and more preferably trialkylphosphines that do not have a substituent. Specific examples of trialkylphosphines that do not have a substituent include trimethylphosphine, triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, tri-n-octadecylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, etc., among which tricycloalkylphosphines are more preferred, and tricyclohexylphosphine is particularly preferred.

[0058] In the above general formulas (1) and (2), R 1 , R 2 , X 1 , X 2 , L 1 and L 2 The ligands may be bonded to each other individually and / or in any combination to form a multidentate chelate ligand.

[0059] In addition, the metathesis polymerization catalyst used in the present invention is preferably L 1 is a compound represented by the above general formula (3) or (4), L 2Specific examples of the compounds represented by the general formula (3) or (4) include 1,3-bis(1-adamantyl)imidazolidin-2-ylidene, 1,3-di-mesityl-octahydrobenzimidazol-2-ylidene, 1,3-bis(1-phenylethyl)-4-imidazolin-2-ylidene, 1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5-ylidene, 1,3-di-isopropyl-2-imidazolidin-2-ylidene, Cyclohexylhexahydropyrimidin-2-ylidene, N,N,N',N'-tetraisopropylcarboxamidine-2-ylidene, benzyl (1,3-dimesityl imidazolidin-2-ylidene), 1,3-dimesityl imidazolidin-2-ylidene, 1,3-dicyclohexyl imidazolidin-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene, etc. Among these, 1,3-dimesityl imidazolidin-2-ylidene is preferred.

[0060] The metathesis polymerization catalyst used in the present invention is a ruthenium carbene complex represented by the above general formula (1) or the general formula (2), 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-di-mesitylene imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-di-mesitylene imidazolidin-2-ylidene) (3-methyl-2-butene-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-di-mesitylene octahydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (Tricyclohexylphosphine) ruthenium dichloride, benzal (1,3-di-mesityl-2,3-dihydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzal (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzal (1,3-di-mesityl-imidazolidine-2-ylidene) pyridine ruthenium dichloride, etc. Among these, from the viewpoint of making the effect of the present invention more significant, benzal (1,3-di-mesityl imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and (1,3-di-mesityl imidazolidin-2-ylidene) (3-methyl-2-butene-1-ylidene) (tricyclohexylphosphine) ruthenium dichloride are preferred.

[0061] The content of the metathesis polymerization catalyst is preferably 0.005 mmol or more, more preferably 0.01 to 50 mmol, further preferably 0.015 to 20 mmol, and particularly preferably 1 to 3 mmol, relative to the total amount of the polymerizable monomers used in the reaction of 1 mol. In addition, the content of the metathesis polymerization catalyst by weight relative to the total amount of the polymerizable monomers used in the reaction of 10,000 parts by mass is preferably 0.004 parts by mass or more, more preferably 0.008 to 45 parts by mass, further preferably 0.012 to 20 parts by mass, and particularly preferably 0.8 to 2.5 parts by mass.

[0062] The polymerizable composition of the present invention is a polymerizable composition containing a coordination compound containing a phosphorus atom, and the content of the coordination compound containing a phosphorus atom is 170 to 2000 moles in terms of phosphorus atoms relative to 1 mole of ruthenium atoms in the metathesis polymerization catalyst. According to the present invention, by including 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 a metathesis polymerization catalyst, the curing time can be controlled within an appropriate range, thereby achieving excellent operability (excellent operability when filling a metal mold, etc.).

[0063] The coordination compound containing a phosphorus atom may be any compound that contains a phosphorus atom and has coordination properties and functions as a Lewis base. From the viewpoint of further improving the effects of the present invention, a compound represented by the following general formula (5) is preferred.

[0064] [Chemical formula 6]

[0065]

[0066] In the above general formula (5), R 9 ~R 11 Each is independently an alkyl group which may have a substituent, or an aryl group which may have a substituent. Among these, an aryl group which may have a substituent is preferred, and examples of the aryl group which may have a substituent include: an unsubstituted aryl group such as phenyl; an aryl group having an electron-donating group as a substituent such as tolyl, methoxyphenyl, ethoxyphenyl, etc. In the above general formula (5), R 9 ~R 11 The groups may be the same or different from each other, or may be a polyvalent phosphine formed via an alkylene group.

[0067] The polyvalent phosphine is preferably a compound represented by the following general formula, for example.

[0068] [Chemical formula 7]

[0069]

[0070] In the above general formula (5'), R 12 , R 13 , R 15 , 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, and n is an integer greater than or equal to 2. 12 , R 13 , R 15 , R 16 , preferably an aryl group which may have a substituent, and examples of the aryl group which may have a substituent include: an unsubstituted aryl group such as phenyl; an aryl group having an electron-donating group as a substituent such as tolyl, methoxyphenyl, ethoxyphenyl, etc. 14 , preferably an alkylene group having 1 to 6 carbon atoms, 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.

[0071] The compound represented by the general formula (5) is not particularly limited, and 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, 1,4-bis(diphenylphosphinobutane), and the like. The compound represented by the general formula (5) may be used alone or in combination of two or more. Among these, triphenylphosphine, trimethoxyphenylphosphine, 1,2-bis(diphenylphosphino)ethane, and 1,4-bis(diphenylphosphinobutane) are preferred, and a combination of triphenylphosphine and trimethoxyphenylphosphine is more preferred. When triphenylphosphine and trimethoxyphenylphosphine are used in combination, the molar ratio of "triphenylphosphine:trimethoxyphenylphosphine" calculated in terms of phosphorus atom is preferably 1:2 to 10:1, and more preferably 1:1 to 5:1.

[0072] The content of the coordination compound containing phosphorus atoms 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, relative to 1 mole of ruthenium atoms in the metathesis polymerization catalyst in terms of phosphorus atoms. In addition, the content of the coordination compound containing phosphorus atoms in the polymerizable composition of the present invention in terms of weight conversion is preferably 54 to 320 parts by mass, more preferably 55 to 270 parts by mass, and further preferably 56 to 220 parts by mass relative to 1 part by mass of the metathesis polymerization catalyst. When the content of the coordination compound containing phosphorus atoms is too small, the curing time is shortened and the operability is deteriorated. On the other hand, when the content of the coordination compound containing phosphorus atoms is too large, there is a problem that the catalytic activity is insufficient and the polymerization reaction cannot be fully carried out.

[0073] Furthermore, the polymerizable composition of the present invention may contain a radical generator, a diisocyanate compound, a polyfunctional (meth)acrylate compound, a coupling agent, and other optional components as desired.

[0074] The free radical generator has the function of generating free radicals by heating, thereby initiating a crosslinking reaction in the norbornene-based resin. The portion where the free radical generator initiates the crosslinking reaction is mainly the carbon-carbon double bond contained in the norbornene-based resin, but sometimes the saturated bond portion also undergoes crosslinking. Examples of the free radical generator include organic peroxides, diazo compounds, and non-polar free radical generators.

[0075] The content of the radical generator in the polymerizable composition of the present invention is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomers.

[0076] Examples of the diisocyanate compound include 4,4′-methylenediphenyl 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, toluene diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, and 4,4′-diisocyanate. Aromatic diisocyanate compounds such as benzyl diisocyanate; 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, etc., polyurethane prepolymers obtained by reacting these diisocyanate compounds with low molecular weight polyols and polyamines in a manner that the ends become isocyanates, etc. In addition, polyfunctional compounds having isocyanate groups that are obtained by converting these compounds into isocyanurate bodies, biuret bodies, adducts, or polymers, which are known compounds that have been used in the past, can be used without particular limitation. Examples of such compounds include dimers of 2,4-toluene diisocyanate, triphenylmethane triisocyanate, tris(p-isocyanatephenyl)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. Among these, aromatic diisocyanate compounds, aliphatic diisocyanate compounds, and alicyclic diisocyanate compounds, which are polyfunctional non-blocked isocyanate compounds, are preferably used from the perspective of being easy to obtain and easy to handle.

[0077] These compounds can be used alone or in combination of two or more.

[0078] In addition, a multifunctional blocked isocyanate compound refers to a compound that is inactive at room temperature by reacting at least two isocyanate groups in the molecule with a compound containing active hydrogen. The isocyanate compound generally has a structure in which the isocyanate group is masked by a blocking agent such as alcohols, phenols, ε-caprolactam, oximes, and active methylene compounds. The multifunctional blocked isocyanate compound generally does not react at room temperature, so it has excellent storage stability, and generally generates an isocyanate group again by heating at 140 to 200° C., which can show excellent reactivity.

[0079] The diisocyanate compound can 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 relative to 100 parts by mass of the total amount of the polymerizable monomers used in the reaction.

[0080] In addition, from the viewpoint of further improving the bonding strength to other materials when the norbornene-based resin is compounded with other materials, a multifunctional (meth)acrylate compound can be used. It is inferred that by using a multifunctional (meth)acrylate compound together with a diisocyanate compound, the active hydrogen reactive group of the diisocyanate compound forms a chemical bond with the hydroxyl group present in the multifunctional (meth)acrylate compound, thereby further improving the bonding strength to other materials. As multifunctional (meth)acrylate compounds, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and neopentyl glycol dimethacrylate can be cited as preferred examples.

[0081] The multifunctional (meth)acrylate compound can be used alone or in combination of two or more. The amount of the multifunctional (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 relative to 100 parts by mass of the total amount of the polymerizable monomers used in the reaction.

[0082] The coupling agent is not particularly limited, but from the viewpoint of improving the adhesion to other materials when the norbornene-based resin is compounded with other materials, a silane coupling agent having at least one hydrocarbon group having a norbornene structure (norbornene skeleton) is preferred. Specific examples of the silane coupling agent include bicycloheptenyl trimethoxysilane, bicycloheptenyl triethoxysilane, bicycloheptenyl ethyl trimethoxysilane, bicycloheptenyl ethyl triethoxysilane, bicycloheptenyl hexyl trimethoxysilane, bicycloheptenyl hexyl triethoxysilane, etc. Bicycloheptenyl ethyl trimethoxysilane, bicycloheptenyl ethyl triethoxysilane, bicycloheptenyl hexyl trimethoxysilane and bicycloheptenyl hexyl triethoxysilane are preferred, bicycloheptenyl ethyl trimethoxysilane and bicycloheptenyl ethyl triethoxysilane are more preferred, and bicycloheptenyl ethyl trimethoxysilane and bicycloheptenyl ethyl triethoxysilane are further preferred.

[0083] 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% by mass, more preferably 0.3 to 2% by mass, and even more preferably 0.5 to 1% by mass.

[0084] The polymerizable composition of the present invention may also contain a silane coupling agent having no hydrocarbon group having a norbornene structure; or a coupling agent other than the silane coupling agent such as a thiol coupling agent, an aluminate coupling agent, a titanate coupling agent, or a fatty acid ester.

[0085] Examples of other optional components include activators, elastomers, antioxidants (antiaging agents), colorants, light stabilizers, flame retardants, and the like.

[0086] The activator is a compound that acts as a co-catalyst for the metathesis polymerization catalyst and improves the polymerization activity of the catalyst. As the activator, for example, alkylaluminum halides such as ethylaluminum dichloride and diethylaluminum chloride; alkoxyalkylaluminum halides in which a part of the alkyl groups of these alkylaluminum halides are substituted with alkoxy groups; organic tin compounds, etc. can be used. The amount of the activator used is not particularly limited, but is preferably 0.1 to 100 moles, more preferably 1 to 10 moles, relative to 1 mole of the total metathesis polymerization catalyst used in the polymerizable composition.

[0087] As elastomers, for example, 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 their hydrogenated products can be cited. By dissolving the elastomer in the polymerizable composition for use, its viscosity can be adjusted. In addition, by adding an elastomer, the impact resistance of the norbornene-based resin formed by the bulk polymerization of the composition can be improved. The amount of the elastomer used is preferably 0.5 to 20 parts by mass, more preferably 2 to 10 parts by mass, relative to the total amount of 100 parts by mass of the polymerizable monomer in the polymerizable composition.

[0088] Examples of the antioxidant include various antioxidants for plastics and rubber, such as phenol-based, phosphorus-based, and amine-based antioxidants.

[0089] As the coloring agent, dyes, pigments, etc. can be used. The types of dyes are various, and known dyes can be appropriately selected and used. In addition, as pigments, for example, carbon black, graphite, chrome yellow, yellow iron oxide, titanium dioxide, zinc oxide, lead tetraoxide, red lead, chromium oxide, Prussian blue, titanium black, etc. can be cited.

[0090] Examples of the light stabilizer include benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, salicylate ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, N,N′-oxalyl dianilide ultraviolet absorbers, hindered amine ultraviolet absorbers, and benzoate ultraviolet absorbers.

[0091] Examples of the flame retardant include phosphorus-based flame retardants, nitrogen-based flame retardants, halogen-based flame retardants, and metal hydroxide-based flame retardants such as aluminum hydroxide and magnesium hydroxide.

[0092] Furthermore, a filler may be blended into the polymerizable composition of the present invention as an optional component. As the filler, various fillers can be used without particular limitation, but a granular inorganic filler is preferably used.

[0093] The granular inorganic filler preferably has an aspect ratio of 1 to 2, and more preferably has an aspect ratio of 1 to 1.5. In addition, the 50% volume cumulative diameter of the granular inorganic filler is preferably 0.1 to 50 μm, more preferably 1 to 30 μm, and particularly preferably 1 to 10 μm. Here, 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 a number average major axis diameter calculated as the arithmetic mean of the major axis diameters of 100 randomly selected fillers in an optical microscope photograph. In addition, the 50% volume cumulative diameter is a value obtained by measuring the particle size distribution using an X-ray transmission method.

[0094] Specific examples of granular inorganic fillers include calcium carbonate, calcium hydroxide, calcium silicate, calcium sulfate, aluminum hydroxide, magnesium hydroxide, titanium oxide, zinc oxide, barium titanate, silicon dioxide, aluminum oxide, gadolinium oxide, carbon black, graphite, antimony oxide, red phosphorus, various metal powders, metal alloy powders, clay, various ferrites, hydrotalcite, etc. Among these, magnesium hydroxide, aluminum hydroxide, silicon dioxide, and aluminum oxide are preferred, and aluminum hydroxide and silicon dioxide are particularly preferred.

[0095] The granular inorganic filler can be a material after the surface is hydrophobized. By using the granular inorganic filler after the hydrophobization, the condensation and precipitation of the granular inorganic filler in the polymerizable composition can be prevented, and in addition, the dispersion of the granular inorganic filler in the obtained norbornene resin can be uniform. Moreover, the result can further improve the strength of the norbornene resin. As the treatment agent used in the hydrophobization, fatty acids, greases, surfactants, waxes, etc. such as silane coupling agents, titanate coupling agents, aluminum coupling agents, stearic acid, etc. can be cited. In addition, the treatment agent used in the hydrophobization can be reacted with the granular inorganic filler in advance and its surface is hydrophobized, or it can also be the following mode: the treatment agent used in the hydrophobization is not reacted with the granular inorganic filler in advance, it is matched in the polymer composition, and the surface of the granular inorganic filler is hydrophobized in the polymer composition.

[0096] The amount of the particulate inorganic filler contained in the polymerizable composition of the present invention is preferably 10 to 1000 parts by mass, more preferably 100 to 500 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomers.

[0097] In addition, the polymerizable composition of the present invention may contain a fibrous inorganic filler in addition to a granular inorganic filler. As the fibrous inorganic filler, a fibrous inorganic filler having an aspect ratio of 5 to 100 is preferred, and a fibrous inorganic filler having an aspect ratio of 10 to 50 is more preferred. In addition, the 50% volume cumulative diameter of the fibrous inorganic filler is preferably 0.1 to 50 μm, and more preferably 1 to 30 μm.

[0098] As the specific example of fibrous inorganic filling material, glass fiber, wollastonite, potassium titanate, vermiculite, basic magnesium sulfate, aluminum borate, tetrapinal zinc oxide, gypsum fiber, phosphate fiber, alumina fiber, whisker-like calcium carbonate, whisker-like boehmite etc. can be enumerated. Among these, preferably wollastonite and whisker-like calcium carbonate. In addition, fibrous inorganic filling material can be the fibrous inorganic filling material after its surface is hydrophobized similarly to the above-mentioned granular inorganic filling material.

[0099] The polymerizable composition of the present invention can be prepared by appropriately mixing the above-mentioned components according to a known method. The polymerizable composition of the present invention can be prepared in the following manner: two or more pre-formulated liquids are prepared in advance, and before the norbornene-based resin is about to be made, the two or more pre-formulated liquids are mixed using a mixing device or the like. The above-mentioned components are divided into two or more liquids to prepare the pre-formulated liquid, so that bulk polymerization is not carried out when there is only one liquid, and when all the liquids are mixed, a polymerizable composition containing each component in a prescribed ratio (the total content of each component is 100% by mass) is formed. As a combination of such two or more reaction stock solutions, depending on the type of metathesis polymerization catalyst used, the following two types (a) and (b) can be cited.

[0100] (a): As the above-mentioned metathesis polymerization catalyst, it is possible to use a metathesis polymerization catalyst that does not have polymerization reaction activity when alone, but shows polymerization reaction activity by using an activator in combination. In this case, it is possible to use a pre-prepared liquid (A liquid) containing a polymerizable monomer containing a norbornene-based monomer and an activator and a pre-prepared liquid (B liquid) containing a polymerizable monomer containing a norbornene-based monomer and a metathesis polymerization catalyst, and mix them to obtain a polymerizable composition. Furthermore, it is also possible to use a pre-prepared liquid (C liquid) containing a polymerizable monomer containing a norbornene-based monomer and not including any of a metathesis polymerization catalyst and an activator. In addition, at this time, the coordination compound containing a phosphorus atom can be included in any pre-prepared liquid, but from the viewpoint of being able to improve the storage stability of the metathesis polymerization catalyst, it is preferably at least included in the pre-prepared liquid (B liquid).

[0101] (b): In addition, when a metathesis polymerization catalyst having polymerization reaction activity alone is used as a metathesis polymerization catalyst, a polymerizable composition can be obtained by mixing a pre-formulated liquid (i) containing a polymerizable monomer containing a norbornene-based monomer with a pre-formulated liquid (ii) containing a metathesis polymerization catalyst. At this time, as the pre-formulated liquid (ii), a pre-formulated liquid in which the metathesis polymerization catalyst is dissolved or dispersed in a small amount of an inactive solvent is generally used. As such a solvent, for example: 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, ethyl acetate, etc.

[0102] In addition, in this case, the coordination compound containing a phosphorus atom may be contained in any pre-formulated solution, but from the viewpoint of being able to improve the storage stability of the metathesis polymerization catalyst, it is preferably contained in at least the pre-formulated solution (ii), and more preferably contained in both the pre-formulated solution (i) and the pre-formulated solution (ii). In this case, the content ratio of the coordination compound containing a phosphorus atom is preferably 1:0.01 to 1:10, more preferably 1:0.1 to 1:9, and further preferably 1:0.2 to 1:8 in terms of the weight ratio of "the amount of the coordination compound containing a phosphorus atom contained in the pre-formulated solution (i) (monomer solution) : the amount of the coordination compound containing a phosphorus atom contained in the pre-formulated solution (ii) (catalyst solution)".

[0103] Optional components such as a radical initiator, a diisocyanate compound, and a polyfunctional (meth)acrylate compound may be contained in any of the above-mentioned pre-formulated liquids, or may be added in the form of a mixed liquid other than the above-mentioned pre-formulated liquids.

[0104] The premixed liquids may be mixed directly or by using a low-pressure mixer or mixing device such as a dynamic mixer or a static mixer, other than a collision mixer generally used in reaction injection molding.

[0105] <Norbornene-based resin>

[0106] The norbornene-based resin of the present invention is obtained by bulk polymerization of the polymerizable composition of the present invention.

[0107] Examples of methods for producing the norbornene-based resin of the present invention include a method in which the two or more pre-mixed liquids are introduced separately into a collision mixing device, mixed instantly in a mixing head, and bulk polymerized in a mold or on a substrate.

[0108] There is no particular limitation on the molding mold, and for example, a metal mold formed by a male mold and a female mold can be used. In addition, the mold used does not necessarily have to be an expensive metal mold with high rigidity, and is not limited to a metal mold. A resin mold or just a mold frame can be used. There is no particular limitation on the material used for the metal mold, and examples include steel, aluminum, zinc alloy, nickel, copper, chromium, etc. The mold can be manufactured by any method including casting, forging, thermal spraying, electroforming, etc., and can also be a plated mold. The structure of the mold is preferably determined in consideration of the pressure when the polymerizable composition is injected into the mold. In addition, the clamping pressure of the metal mold is generally about 0.1 to 9.8 MPa in terms of gauge pressure.

[0109] The mold temperature may be appropriately selected depending on the type of the norbornene-based monomer used, and is preferably a temperature 5° C. or higher than the freezing point of the norbornene-based monomer, and more preferably a temperature 10° C. or higher than the freezing point.

[0110] After the polymerizable composition becomes non-flowable during bulk polymerization, the mold is preferably heated to cure in two stages in order to fully polymerize and obtain desired mechanical properties. The heating temperature is preferably 90 to 200°C, more preferably 100 to 170°C, and even more preferably 110 to 150°C.

[0111] Examples of methods for adjusting the mold temperature include adjusting the mold temperature with a heater and adjusting the temperature of a medium such as cold temperature-controlled water or oil that circulates through a pipe buried inside the mold.

[0112] After the bulk polymerization is completed, the norbornene-based resin can be obtained by, for example, opening and demolding the mold.

[0113] Example

[0114] Hereinafter, the present invention will be described based on Examples, but the present invention is not limited to these Examples. In addition, "parts" and "%" are based on mass unless otherwise specified.

[0115] <Example 1>

[0116] (Preparation of Catalyst Solution)

[0117] Two parts of a ruthenium carbene complex (benzylidene (1,3-di-mesitylphenylimidazolidine-2-ylidene) (tricyclohexylphosphine) dichlororuthenium, C848) represented by the following formula (6) as a metathesis polymerization catalyst and 100 parts of triphenylphosphine (TPP) were dissolved in 100 parts of cyclopentanone to prepare a catalyst solution. The prepared catalyst solution was stored at 25° C. under a nitrogen atmosphere for 1 month. In addition, the amount of triphenylphosphine in the obtained catalyst solution calculated in terms of phosphorus atoms was 162 mol relative to 1 mol of ruthenium in the ruthenium carbene complex represented by the following formula (6).

[0118] [Chemical formula 8]

[0119]

[0120] (Preparation of polymerizable composition and measurement of curing time)

[0121] Next, differently from the above, 100 parts of triphenylphosphine (TPP) were added to 10,000 parts of RIM monomer (manufactured by Japan Zeon Co., Ltd.) to prepare a monomer solution. Then, the whole amount of the obtained monomer solution and the whole amount of the above catalyst solution stored for 1 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 determination of the curing time was carried out under the condition of an initial temperature of 30°C, and the time when the measured temperature became 100°C due to the heat generated by the polymerization was taken as the curing time. The results are shown in Table 1. In addition, the composition of the above RIM monomer consists of about 90 parts of dicyclopentadiene and about 10 parts of tricyclopentadiene (consisting of about 90% of dicyclopentadiene and about 10% of tricyclopentadiene). In addition, the amount of triphenylphosphine in the obtained polymerizable composition calculated in terms of phosphorus atoms is 324 moles relative to 1 mole of ruthenium in the ruthenium carbene complex represented by the above formula (6).

[0122] <Example 2>

[0123] The catalyst solution obtained in the same manner as in Example 1 was stored for 1 month under the same conditions as in Example 1. In addition, 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. Then, the entire amount of the obtained monomer solution was mixed with the entire amount of the catalyst solution stored for 1 month 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.

[0124] The amount of triphenylphosphine in the obtained polymerizable composition in terms of phosphorus atom was 405 mol per 1 mol of ruthenium in the ruthenium carbene complex represented by the above formula (6).

[0125] <Example 3>

[0126] The catalyst solution obtained in the same manner as in Example 1 was stored for 1 month under the same conditions as in Example 1. In addition, 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. Then, the entire amount of the obtained monomer solution was mixed with the entire amount of the catalyst solution stored for 1 month 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.

[0127] The amount of triphenylphosphine in the obtained polymerizable composition in terms of phosphorus atom was 485 mol per 1 mol of ruthenium in the ruthenium carbene complex represented by the above formula (6).

[0128] <Comparative Example 1>

[0129] The catalyst solution obtained in the same manner as in Example 1 was stored for 1 month under the same conditions as in Example 1. In addition, a monomer solution 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 solution was mixed with the entire amount of the catalyst solution stored for 1 month 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.

[0130] The amount of triphenylphosphine in the obtained polymerizable composition in terms of phosphorus atom was 162 mol per 1 mol of ruthenium in the ruthenium carbene complex represented by the above formula (6).

[0131] [Table 1]

[0132] Table 1

[0133]

[0134] "Catalyst (C848)" is benzylidene (1,3-dimesityl imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride,

[0135] "TPP" is triphenylphosphine.

[0136] As shown in Table 1, by making the amount of triphenylphosphine (TPP) as a coordination compound containing phosphorus atoms in terms of phosphorus atoms in the range of 170 to 1000 mol relative to 1 mol of ruthenium in the ruthenium carbene complex, the curing time of the obtained polymerizable composition is sufficiently extended to more than 400 seconds, and the curing reaction also occurs sufficiently, which can achieve excellent operability (Examples 1 to 3).

[0137] On the other hand, a polymerizable composition in which the amount of triphenylphosphine (TPP) as a coordination compound containing phosphorus atoms is less than 170 mol relative to 1 mol of ruthenium in the ruthenium carbene complex in terms of phosphorus atoms has a short curing time and poor workability (Comparative Example 1).

[0138] <Example 4>

[0139] (Preparation of Catalyst Solution)

[0140] Two parts of a ruthenium carbene complex ((1,3-di-mesitylphenylimidazolidine-2-ylidene)(3-methyl-2-butene-1-ylidene)(tricyclopentylphosphine)dichlororuthenium, C827) represented by the following formula (7) as a metathesis polymerization catalyst and 100 parts of triphenylphosphine (TPP) were dissolved in 100 parts of cyclopentanone to prepare a catalyst solution. The prepared catalyst solution was stored at 25° C. under a nitrogen atmosphere for 6 months. In addition, the amount of triphenylphosphine in the obtained catalyst solution calculated on a phosphorus atom basis was 158 mol relative to 1 mol of ruthenium in the ruthenium carbene complex represented by the following formula (7).

[0141] [Chemical formula 9]

[0142]

[0143] (Preparation of polymerizable composition and measurement of curing time)

[0144] Next, differently from the above, 200 parts of triphenylphosphine (TPP) were added to 10,000 parts of RIM monomer (manufactured by Japan Zeon Co., Ltd.) to prepare a monomer solution. Then, half of the obtained monomer solution and half of the above catalyst solution stored for 6 months 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 determination of the curing time was carried out under the condition of an initial temperature of 30°C, and the time when the measured temperature became 100°C due to the heat generated by the polymerization was taken as the curing time. The results are shown in Table 2. In addition, the composition of the above RIM monomer consists of about 90 parts of dicyclopentadiene and about 10 parts of tricyclopentadiene (consisting of about 90% of dicyclopentadiene and about 10% of tricyclopentadiene). In addition, the amount of triphenylphosphine in the obtained polymerizable composition calculated in terms of phosphorus atoms is 473 moles relative to 1 mole of ruthenium in the ruthenium carbene complex represented by the above formula (6).

[0145] (Manufacture of norbornene-based resin)

[0146] A metal mold made of aluminum 5052 with internal dimensions of 300 mm in length, 250 mm in width, and 4 mm in depth after demolding was prepared, and a flat plate made of aluminum 5052 was used as a lid. Next, after the mold was set to 25°C, the remaining part of the monomer solution obtained above was mixed with the remaining part of the catalyst solution stored for 6 months, and the mold was filled. After the mold was left for 1 hour, the mold was heated to 120°C and left for 1 hour. Next, after the mold was cooled to room temperature, the norbornene-based resin was obtained by demolding.

[0147] The flexural strength, flexural modulus, HDT (edgewise), and heating loss of the obtained norbornene-based resin were measured by the following methods.

[0148] Flexural strength, flexural modulus

[0149] The flexural strength and flexural modulus were measured using a universal testing machine AG5000 (manufactured by Shimadzu Corporation) in accordance with ISO178.

[0150] HDT (edge)

[0151] The HDT (edge) was measured using a HDT measuring apparatus manufactured by Toyo Seiki Co., Ltd. in accordance with ISO75-2.

[0152] Heating loss

[0153] TG / DTA measurement was performed using TG / DTA6200 (manufactured by Hitachi High-Tech Sciences, Ltd.) at a temperature increase rate of 20°C / min, and the weight loss was measured up to 150°C with 30°C as the reference.

[0154] <Example 5>

[0155] 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. In addition, a monomer solution was obtained in the same manner as in Example 4 except that 50 parts of trimethoxyphenylphosphine (TMPP) was added instead of 200 parts of triphenylphosphine (TPP). Then, the entire amount of the obtained monomer solution was mixed with the entire amount of the catalyst solution 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 4. The results are shown in Table 2.

[0156] The total amount of triphenylphosphine and trimethoxyphenylphosphine in the obtained polymerizable composition in terms of phosphorus atoms was 217 mol per 1 mol of ruthenium in the ruthenium carbene complex represented by the above formula (7).

[0157] <Example 6>

[0158] 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. In addition, a monomer solution was obtained in the same manner as in Example 4 except that 100 parts of trimethoxyphenylphosphine (TMPP) was added instead of 200 parts of triphenylphosphine (TPP). Then, the entire amount of the obtained monomer solution was mixed with the entire amount of the catalyst solution 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 4. The results are shown in Table 2.

[0159] The total amount of triphenylphosphine and trimethoxyphenylphosphine in the obtained polymerizable composition in terms of phosphorus atoms was 275 mol per 1 mol of ruthenium in the ruthenium carbene complex represented by the above formula (7).

[0160] <Example 7>

[0161] 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. In addition, a monomer solution was obtained in the same manner as in Example 4 except that 150 parts of trimethoxyphenylphosphine (TMPP) was added instead of 200 parts of triphenylphosphine (TPP). Then, the entire amount of the obtained monomer solution was mixed with the entire amount of the catalyst solution 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 4. The results are shown in Table 2.

[0162] The total amount of triphenylphosphine and trimethoxyphenylphosphine in the obtained polymerizable composition in terms of phosphorus atoms was 334 mol per 1 mol of ruthenium in the ruthenium carbene complex represented by the above formula (7).

[0163] <Example 8>

[0164] 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. In addition, a monomer solution was obtained in the same manner as in Example 4 except that 200 parts of trimethoxyphenylphosphine (TMPP) was added instead of 200 parts of triphenylphosphine (TPP). Then, the entire amount of the obtained monomer solution was mixed with the entire amount of the catalyst solution 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 4. The results are shown in Table 2.

[0165] The total amount of triphenylphosphine and trimethoxyphenylphosphine in the obtained polymerizable composition in terms of phosphorus atoms was 393 mol per 1 mol of ruthenium in the ruthenium carbene complex represented by the above formula (7).

[0166] <Example 9>

[0167] 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. In addition, a monomer solution was obtained in the same manner as in Example 4 except that 50 parts of trimethoxyphenylphosphine (TMPP) were further added together with 200 parts of triphenylphosphine (TPP). Then, the entire amount of the obtained monomer solution was mixed with the entire amount of the catalyst solution 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 4. The results are shown in Table 2.

[0168] The total amount of triphenylphosphine and trimethoxyphenylphosphine in the obtained polymerizable composition in terms of phosphorus atoms was 532 mol per 1 mol of ruthenium in the ruthenium carbene complex represented by the above formula (7).

[0169] <Example 10>

[0170] 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. In addition, a monomer solution was obtained in the same manner as in Example 4 except that 100 parts of trimethoxyphenylphosphine (TMPP) was further added while adding 200 parts of triphenylphosphine (TPP). Then, half of the obtained monomer solution was mixed with half of the catalyst solution 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 4. In addition, using the remaining part of the obtained monomer solution and the remaining part of the catalyst solution stored for 6 months, a norbornene-based resin was obtained in the same manner as in Example 4, and the evaluation was performed in the same manner. The results are shown in Table 2.

[0171] The total amount of triphenylphosphine and trimethoxyphenylphosphine in the obtained polymerizable composition in terms of phosphorus atoms was 591 mol per 1 mol of ruthenium in the ruthenium carbene complex represented by the above formula (7).

[0172] <Example 11>

[0173] The catalyst solution obtained in the same manner as in Example 4 was stored under the same conditions as in Example 4 for 6 months. In addition, a monomer solution was obtained in the same manner as in Example 4 except that 200 parts of 1,4-bis(diphenylphosphinobutane) (DPPB) was added instead of 200 parts of triphenylphosphine (TPP). Then, half of the obtained monomer solution was mixed with half of the catalyst solution 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 4. In addition, using the remaining part of the obtained monomer solution and the remaining part of the catalyst solution stored for 6 months, a norbornene-based resin was obtained in the same manner as in Example 4, and evaluated in the same manner. The results are shown in Table 2.

[0174] The total amount of triphenylphosphine and 1,4-bis(diphenylphosphinobutane) in the obtained polymerizable composition calculated as phosphorus atoms was 546 mol (the total amount of 168 mol of triphenylphosphine and 433 mol of 1,4-bis(diphenylphosphinobutane)) relative to 1 mol of ruthenium in the ruthenium carbene complex represented by the above formula (7).

[0175] <Comparative Example 2>

[0176] The catalyst solution obtained in the same manner as in Example 4 was stored under the same conditions as in Example 4 for 6 months. In addition, a monomer solution was obtained in the same manner as in Example 4 except that triphenylphosphine (TPP) was not added. Then, half of the obtained monomer solution was mixed with half of the catalyst solution 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 4. In addition, using the remaining part of the obtained monomer solution and the remaining part of the catalyst solution stored for 6 months, a norbornene-based resin was obtained in the same manner as in Example 4, and evaluated in the same manner. The results are shown in Table 2.

[0177] The amount of triphenylphosphine in the obtained polymerizable composition in terms of phosphorus atom was 158 mol per 1 mol of ruthenium in the ruthenium carbene complex represented by the above formula (7).

[0178] [Table 2]

[0179]

[0180] "Catalyst (C827)" is (1,3-dimesityl imidazolidin-2-ylidene)(3-methyl-2-butene-1-ylidene)(tricyclopentylphosphine) ruthenium dichloride,

[0181] "TPP" is triphenylphosphine,

[0182] "TMPP" is trimethoxyphenylphosphine.

[0183] As shown in Table 2, by making the amount of triphenylphosphine calculated on a phosphorus atom basis of triphenylphosphine (TPP) and trimethoxyphenylphosphine (TMPP) as coordination compounds containing phosphorus atoms in the range of 170 to 2000 mol relative to 1 mol of ruthenium in the ruthenium carbene complex, the curing time of the obtained polymerizable composition is sufficiently extended to more than 400 seconds, and the curing reaction also occurs sufficiently, thereby achieving excellent operability (Examples 4 to 11).

[0184] On the other hand, a polymerizable composition in which the amount of triphenylphosphine (TPP) as a coordination compound containing phosphorus atoms is less than 170 mol relative to 1 mol of ruthenium in the ruthenium carbene complex in terms of phosphorus atoms has a short curing time and poor workability (Comparative Example 2).

Claims

1. 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 general formula (2), The content of the coordination compound containing phosphorus atoms is 170 to 2000 mol in terms of phosphorus atoms relative to 1 mol of ruthenium atoms in the metathesis polymerization catalyst. In the general formulas (1) and (2), R 1 and R 2 Each independently represents 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, 1 and X 2 are each independently any anionic ligand, L 1 and L 2 is a carbene compound or phosphine containing a heteroatom, L 1 and L 2 At least one of them is a phosphine.

2. The polymerizable composition according to claim 1, wherein The L 1 is a compound represented by the following general formula (3) or (4), wherein L 2 Phosphine In the general formulas (3) and (4), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each is 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 bond to each other to form a ring.

3. The polymerizable composition according to claim 1 or 2, wherein The phosphine is a trialkylphosphine which may have a substituent.

4. The polymerizable composition according to any one of claims 1 to 3, wherein The coordination compound containing a phosphorus atom is a compound represented by the following general formula (5): In the general formula (5), R 9 ~R 11 Each is independently an alkyl group which may have a substituent, an aryl group which may have a substituent, or a polyvalent phosphine formed via an alkylene group.

5. The polymerizable composition according to any one of claims 1 to 4, wherein The polymerizable composition is formed of two or more preformulated solutions that do not undergo polymerization reaction independently, and the polymerizable composition can be formed by mixing the preformulated solutions. 6 . A norbornene-based resin obtained by bulk polymerization of the polymerizable composition according to claim 1 .

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