Catalyst composition, catalyst liquid, and polymerizable composition

Abstract

Provided is a catalyst composition containing: an N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) represented by general formula (1) or general formula (2); and a ruthenium-containing compound (B) other than the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A). The content ratio of the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) and the ruthenium-containing compound (B) is such that, in terms of mass ratio, N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) : ruthenium-containing compound (B) is 50:50 to 90:10.

Description

Catalyst composition, catalyst liquid, and polymerizable composition

[0001] The present invention relates to a catalyst composition, a catalyst liquid, and a polymerizable composition, and more particularly to a catalyst composition that can exhibit excellent catalytic activity and has a long usable life, as well as a catalyst liquid and a polymerizable composition that use such a catalyst composition.

[0002] Transition metal carbene complexes, such as ruthenium carbene complexes known as Grubbs' catalysts and molybdenum and tungsten carbene complexes known as Schrock's catalysts, are known as highly active catalysts for metathesis reactions and are widely used.

[0003] For example, Patent Document 1 proposes a production method for obtaining a highly pure ruthenium indenylidene carbene catalyst, which is a type of ruthenium carbene complex.

[0004] Special Publication No. 2015-504565

[0005] However, although the ruthenium indenylidene carbene catalyst obtained by the technique of Patent Document 1 can exhibit excellent catalytic activity, it has problems such as a rapid rate of viscosity increase when a monomer is added, a short curing time and a short usable time, and poor handleability. The present invention has been made in view of these circumstances, and an object of the present invention is to provide a catalyst composition that can exhibit excellent catalytic activity and has a long usable time.

[0006] The present inventors have conducted studies to achieve the above object and have found that a catalyst composition containing a specific N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) and a ruthenium-containing compound (B) other than the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) in a specified ratio has excellent catalytic activity and a long usable life, which has led to the completion of the present invention.

[0007] That is, the present invention provides the following inventions: [1] A catalyst composition containing an N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) represented by the following general formula (1) or (2), and a ruthenium-containing compound (B) other than the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A), wherein the content ratio of the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) to the ruthenium-containing compound (B) is, in mass ratio, N-heterocyclic carbene ligand-containing ruthenium carbene complex (A):ruthenium-containing compound (B) = 50:50 to 90:10. (In the above general formulas (1) and (2), 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; and these groups may have a substituent, and may also be bonded to each other to form a ring. １ and X ２ are each independently any anionic ligand. １ and L ２ is an N-heterocyclic carbene ligand or a neutral electron donor ligand other than an N-heterocyclic carbene ligand, and L １ and L ２ At least one of the above is an N-heterocyclic carbene ligand. [2] The catalyst composition according to [1], wherein the N-heterocyclic carbene ligand is a compound represented by the following general formula (3) or (4): (In the above general formulas (3) and (4), 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, or may be bonded to each other to form a ring.) [3] In the general formula (1) and the general formula (2), L １is a compound represented by the general formula (3) or (4), and L ２ [4] The catalyst composition according to any one of [1] to [3], wherein the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) is a compound represented by the following general formula (5): (In the above general formula (5), PCy ３ represents tricyclohexylphosphine, Mes represents a mesityl group, and R ９ , R １０ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) [5] The catalyst composition according to any one of [1] to [4], which contains, as the ruthenium-containing compound (B), at least a compound represented by the following general formula (6) or general formula (7): (In the above general formulas (6) and (7), R １１ and R １２ 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 also be bonded to each other to form a ring. ３ and X ４ are each independently any anionic ligand. ３ and L ４ is a neutral electron donating ligand other than an N-heterocyclic carbene ligand.) [6] A catalyst solution containing the catalyst composition according to any one of [1] to [5] and a solvent. [7] A polymerizable composition obtained by blending a norbornene-based monomer as a polymerizable monomer with the catalyst composition according to any one of [1] to [5] or the catalyst solution according to [6].

[0008] According to the present invention, it is possible to provide a catalyst composition that can exhibit excellent catalytic activity and has a long usable time, as well as a catalyst liquid and a polymerizable composition that use such a catalyst composition.

[0009] <Catalyst Composition> The catalyst composition of the present invention is a catalyst composition containing an N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) represented by the following general formula (1) or (2), and a ruthenium-containing compound (B) other than the N-heterocyclic carbene ligand-containing ruthenium carbene complex, wherein the content ratio of the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) to the ruthenium-containing compound (B) is in the range of N-heterocyclic carbene ligand-containing ruthenium carbene complex (A):ruthenium-containing compound (B) = 50:50 to 90:10 by mass ratio. (In the above general formulas (1) and (2), 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; and these groups may have a substituent, and may also be bonded to each other to form a ring. １ and X ２ are each independently any anionic ligand. １ and L ２ is an N-heterocyclic carbene ligand or a neutral electron donor ligand other than an N-heterocyclic carbene ligand, and L １ and L ２ At least one of is an N-heterocyclic carbene ligand.

[0010] In the above general formulas (1) and (2), 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; 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 bonded to each other to form a ring include an indenylidene group, such as a phenylindenylidene group, which may have a substituent. The phenylindenylidene group may also have a substituent, such as an alkyl group having 1 to 4 carbon atoms.

[0011] 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, an aryloxy group having 6 to 20 carbon atoms, an aryloxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 8 ... alkyl group having 2 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, an alkyl group having 2 to Examples of the organic group include alkylthio groups, 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, arylsulfonic acid groups having 6 to 20 carbon atoms, phosphonic acid groups, arylphosphonic acid groups having 6 to 20 carbon atoms, alkylammonium groups having 1 to 20 carbon atoms, and arylammonium groups having 6 to 20 carbon atoms. These 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, may have a substituent. Examples of the substituent include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and aryl groups having 6 to 10 carbon atoms.

[0012] In the above general formulas (1) and (2), 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 alkoxyl group, an aryloxy group, and a carboxyl group. A halogen atom is preferred, and a chlorine atom is more preferred.

[0013] In the above general formulas (1) and (2), L １ and L ２ is an N-heterocyclic carbene ligand or a neutral electron donor ligand other than an N-heterocyclic carbene ligand, and L １ and L ２At least one of the N-heterocyclic carbene ligands is an N-heterocyclic carbene ligand and a neutral electron donating ligand other than an N-heterocyclic carbene ligand is a ligand that has a neutral charge when separated from the central metal.

[0014] As the N-heterocyclic carbene ligand, a compound represented by the following general formula (3) or (4) is preferred, and from the viewpoint of improving catalytic activity, a compound represented by the following general formula (3) is more preferred.

[0015] In the above general formulas (3) and (4), R ３ , R ４ , R ５ , R ６ , R ７ and R ８ 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. 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 general formulas (1) and (2) above. 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.

[0016] In addition, the effect of the present invention becomes more remarkable when R ５ , R ６ , R ７ and R ８ , R in the above general formula (4) ５ and R ６ is preferably a hydrogen atom. ３ and R ４ is preferably an aryl group which may have a substituent, more preferably a phenyl group having an alkyl group of 1 to 10 carbon atoms as a substituent, and even more preferably a mesityl group.

[0017] Examples of neutral electron donating ligands other than N-heterocyclic carbene ligands include oxygen atoms, water, carbonyls, ethers, nitriles, esters, phosphinites, phosphites, sulfoxides, thioethers, amides, imines, aromatic compounds, cyclic diolefins, olefins, isocyanides, and thiocyanates. Among these, phosphines are preferred. The phosphines are not particularly limited, and examples thereof include optionally substituted trialkylphosphines and optionally substituted triarylphosphines from the viewpoint of catalytic activity. However, optionally substituted trialkylphosphines are preferred, and unsubstituted trialkylphosphines are more preferred. Specific examples of unsubstituted trialkylphosphines include trimethylphosphine, triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, tri-n-octadecylphosphine, tricyclopentylphosphine, and tricyclohexylphosphine (PCy ３ Among these, tricycloalkylphosphines are more preferred, and tricyclohexylphosphine (PCy ３ ) is particularly preferred.

[0018] In the above general formulas (1) and (2), R １ , R ２ , X １ , X ２ , L １ and L ２ may be linked together alone and / or in any combination to form multidentate chelating ligands.

[0019] The N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) is also １ is a compound represented by the above general formula (3) or (4), and L ２Specific examples of the compound represented by the 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 thereof include imidin-2-ylidene, N,N,N',N'-tetraisopropylformamidinylidene, benzylidene (1,3-dimesitylimidazolidin-2-ylidene), 1,3-dimesitylimidazolidin-2-ylidene, 1,3-dicyclohexylimidazolidin-2-ylidene, 1,3-diisopropyl-4-imidazolin-2-ylidene, and 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene. Among these, 1,3-dimesitylimidazolidin-2-ylidene is preferred.

[0020] As the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A), among the compounds represented by the above general formula (1) or (2), the compound represented by the above general formula (1) is preferred in that the effects of the present invention are more pronounced, and among these, the compound represented by the following general formula (5) is more preferred. ３ represents tricyclohexylphosphine, Mes represents a mesityl group (the same applies to formulas (10) and (11) described later), and R ９ , R １０ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0021] The catalyst composition of the present invention contains, in addition to the above-mentioned N-heterocyclic carbene ligand-containing ruthenium carbene complex (A), a ruthenium-containing compound (B) other than the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A), and the content ratio of the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) to the ruthenium-containing compound (B) is, in mass ratio, in the range of N-heterocyclic carbene ligand-containing ruthenium carbene complex (A):ruthenium-containing compound (B) = 50:50 to 90:10.

[0022] According to the findings of the present inventors, although the above-described N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) can exhibit excellent catalytic activity, it suffers from the problem of a rapid rate of viscosity increase upon addition of a monomer, resulting in short curing and usable lives and poor handleability. In response to this problem, the present inventors conducted extensive research and found that by incorporating a ruthenium-containing compound (B) other than the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) in the above-mentioned predetermined ratio in addition to the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A), it is possible to achieve excellent catalytic activity while reducing the rate of viscosity increase upon addition of a monomer, thereby lengthening the curing and usable lives and, as a result, improving the handleability of the catalyst. Based on these findings, the present inventors have completed the present invention.

[0023] In the catalyst composition of the present invention, the content ratio of the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) to the ruthenium-containing compound (B) is, in terms of the mass ratio of "N-heterocyclic carbene ligand-containing ruthenium carbene complex (A):ruthenium-containing compound (B)," 50:50 to 90:10, preferably 55:45 to 85:15, more preferably 60:40 to 85:15, and particularly preferably 60:40 to 80:20. If the content ratio of the ruthenium-containing compound (B) is too high, the catalytic activity will decrease, while if the content ratio of the ruthenium-containing compound (B) is too low, the curing time and usable life will be shortened, resulting in poor handleability as a catalyst.

[0024] In the catalyst composition of the present invention, the ruthenium-containing compound (B) is not particularly limited as long as it is a compound containing a ruthenium atom other than the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A). However, from the viewpoint of further enhancing the catalytic activity and extending the usable life, it is preferable that the ruthenium-containing compound (B) contains at least a compound represented by the following general formula (6) or general formula (7): (In the above general formulas (6) and (7), R １１ and R １２ 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 also be bonded to each other to form a ring. ３ and X ４ are each independently any anionic ligand. ３ and L ４ is a neutral electron donating ligand other than an N-heterocyclic carbene ligand.

[0025] In the above general formulas (6) and (7), R ３ and R ４ 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. 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 the above-mentioned R １ and R ２ The same can be mentioned.

[0026] In the above general formulas (6) and (7), X ３ and X ４ Each of X independently represents an anionic ligand. １ and X ２ The same can be mentioned.

[0027] In the above general formulas (6) and (7), L ３ and L ４ is a neutral electron donating ligand other than an N-heterocyclic carbene ligand. The neutral electron donating ligand other than an N-heterocyclic carbene ligand includes the above-mentioned L １ and L ２ The compounds represented by the general formula (6) or (7) can also be the same as those represented by the general formula (6) or (7) above. ３ and L ４ is preferably a phosphine.

[0028] In the above general formulas (6) and (7), R １１ , R １２ , X ３ , X ４ , L ３ and L ４ may be linked together alone and / or in any combination to form multidentate chelating ligands.

[0029] When the ruthenium-containing compound (B) contains at least a compound represented by the general formula (6) or (7), it is more preferable to contain at least a compound represented by the general formula (6). In addition, when the ruthenium-containing compound (B) contains at least a compound represented by the general formula (6) or (7), the effects of the present invention become more pronounced. Therefore, the compound represented by the general formula (6) or (7) is preferably a compound having a structure similar to that of the compound represented by the general formula (1) or (2), in relation to the compound represented by the general formula (1). １１ =R １ , R １２ =R ２ , X ３ =X １ , X ４ =X ２ A compound having the relationship: ２ When L is a neutral electron donor ligand other than an N-heterocyclic carbene ligand, ３ =L ４ =L ２That is, the compound represented by the general formula (6) or (7) is preferably the same compound as the compound represented by the general formula (1) or (2), except that it has a neutral electron-donating ligand other than an N-heterocyclic carbene ligand instead of the N-heterocyclic carbene ligand.

[0030] In the catalyst composition of the present invention, the ruthenium-containing compound (B) may be, in addition to the compound represented by the general formula (6) or (7), ruthenium oxide (RuO ２ , RuO ４ ) may also be included.

[0031] In the catalyst composition of the present invention, the content of the compound represented by the above general formula (6) or general formula (7) in the ruthenium-containing compound (B) is not particularly limited, but is preferably 10 to 50 mass%, more preferably 10 to 40 mass%, and even more preferably 10 to 30 mass%, relative to 100 mass% of the total amount of the ruthenium-containing compound (B).

[0032] The method for producing the catalyst composition of the present invention is not particularly limited, but it is preferable to adopt the following production method from the viewpoint of being able to simultaneously produce a composition containing, as the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A), a compound represented by the above general formula (1) or (2), and, as the ruthenium-containing compound (B), a compound represented by the above general formula (6) or (7). That is, ３ ) ｎ X １ X ２ (n=3-4) and propargyl alcohol derivative Ph ２ a first step of reacting —C(OH)—C≡C—H in a solvent; and a neutral electron donating ligand L other than an N-heterocyclic carbene ligand to the reaction solution obtained in the first step. ５ Or such a ligand L ５ Compounds that give ３ a second step of adding an N-heterocyclic carbene ligand L to the reaction solution obtained in the second step and reacting the resulting mixture;６ Or such a ligand L ６ and a third step of adding a compound which gives the following formula (I):

[0033] According to the above-described method for producing a catalyst composition, a catalyst composition can be produced in one pot, which simultaneously contains a compound represented by the following general formula (8) as the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) and a compound represented by the following general formula (9) as the ruthenium-containing compound (B). Furthermore, the catalyst composition obtained by the above-described method for producing a catalyst composition may contain, as the ruthenium-containing compound (B), a ruthenium-containing compound other than the compound represented by the following general formula (9). (In the above general formula (8), X １ and X ２ are each independently any anionic ligand, and L ５ is a neutral electron donating ligand other than an N-heterocyclic carbene ligand, and L ６ is an N-heterocyclic carbene ligand. (In the above general formula (9), X １ and X ２ are each independently any anionic ligand, and L ５ is a neutral electron donating ligand other than an N-heterocyclic carbene ligand.

[0034] In the above-described method for producing a catalyst composition, it is preferable to adjust the content ratio of the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) and the ruthenium-containing compound (B) in the obtained catalyst composition by controlling the washing operation and recrystallization operation between Step 1 and Step 2, between Step 2 and Step 3, and further after Step 3. It is preferable not to perform the washing operation and recrystallization operation at least after Step 3, and it is also preferable not to perform either the washing operation or the recrystallization operation between Step 1 and Step 2, between Step 2 and Step 3, and further after Step 3.

[0035] The more these washing and recrystallization operations are performed, the more the proportion of the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) in the obtained catalyst composition tends to increase. In particular, according to the findings of the present inventors, by performing the washing and recrystallization operations after the third step, the proportion of the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) in all ruthenium compounds exceeds 90 mass % in terms of ruthenium, making it impossible to obtain the desired catalyst composition.

[0036] In the method for producing a catalyst composition, in addition to controlling the washing operation and recrystallization operation, the content ratio of the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) and the ruthenium-containing compound (B) in the resulting catalyst composition can also be adjusted by adjusting the type of solvent, the amount of each compound used, and further the reaction temperature and reaction time.

[0037] Further, according to the method for producing the catalyst composition, the ruthenium-containing compound (B) is a compound represented by the general formula (6) or (7), which, in relation to the compound represented by the general formula (1) or (2), satisfies R １１ =R １ , R １２ =R ２ , X ３ =X １ , X ４ =X ２ and L ３ =L ４ =L ２ A catalyst composition containing compounds having the following relationship can be suitably produced.

[0038] In the method for producing the catalyst composition, the first step is to prepare a precursor compound, Ru(PPh ３ ) ｎ X １ X ２ (n=3-4) and propargyl alcohol derivative Ph ２ In the first step, a precursor compound, Ru(PPh ３ )ｎ X １ X ２ and propargyl alcohol derivative Ph ２ -C(OH)-C≡C-H reacts to form Ph ２ A complex compound can be formed in which an indenylidene ring derived from —C(OH)—C≡C—H is coordinated to Ru.

[0039] The precursor compound Ru(PPh ３ ) ｎ X １ X ２ In this case, X １ and X ２ are each independently any anionic ligand, and examples of the anionic ligand include those described above. １ and X ２ is preferably a halogen atom, more preferably a chlorine atom. ３ ) ｎ X １ X ２ In the formula, Ph is a phenyl group, and the phenyl group may have an alkyl group having 1 to 4 carbon atoms as a substituent. Also, n is 3 to 4, preferably 3. That is, the precursor compound Ru(PPh ３ ) ｎ X １ X ２ Examples include Ru(PPh ３ ) ３ Cl ２ is preferred.

[0040] Also, propargyl alcohol derivative Ph ２ In the —C(OH)—C≡C—H, Ph is a phenyl group, and the phenyl group may have an alkyl group having 1 to 4 carbon atoms as a substituent.

[0041] The solvent is not particularly limited, but a polar solvent is preferred, and cyclic monoethers such as tetrahydrofuran, furan, and 2-methylfuran; cyclic diethers such as 1,3-dioxane, 1,4-dioxane, and 5-methyl-1,3-dioxane; etc. can be used. However, from the viewpoint of suitably controlling the content of the ruthenium-containing compound (B) in the resulting catalyst composition within the above-mentioned range, it is preferable to use a cyclic monoether, and it is more preferable to use tetrahydrofuran. The amount of the solvent used is not particularly limited, but it is preferable to use a polar solvent such as a cyclic monoether, and it is more preferable to use tetrahydrofuran, ３ ) ｎ X １ X ２ The amount is preferably 500 to 6,000 parts by mass, and more preferably 1,000 to 5,200 parts by mass, per 100 parts by mass.

[0042] In the first step, it is preferable to use an acid catalyst. The acid catalyst is not particularly limited, but examples thereof include protonic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, and nitric acid. In addition, a compound that becomes an acid when contacted with water, such as acetyl chloride, may be used. The amount of the acid catalyst used is determined based on the amount of Ru(PPh ３ ) ｎ X １ X ２ The amount is preferably 3 to 6 parts by mass, and more preferably 2.5 to 5.8 parts by mass, per 100 parts by mass.

[0043] In the first step, the reaction temperature is preferably 10 to 70° C., more preferably 60 to 70° C., and the reaction time is 1.5 to 128 hours, more preferably 1.5 to 2.5 hours.

[0044] Next, in the second step, the reaction solution obtained in the first step is treated with a neutral electron donating ligand L other than an N-heterocyclic carbene ligand. ５ (However, PPh ３ or such ligands L ５ In the second step, a compound which gives PPh coordinated to Ru is added and reacted. ３ L ５ This results in Ru being replaced by L５ can form a complex compound in which

[0045] L ５ is a neutral electron donating ligand other than an N-heterocyclic carbene ligand, and as such a neutral electron donating ligand other than an N-heterocyclic carbene ligand, those mentioned above can be used.

[0046] In the second step, the reaction mixture obtained in the first step is directly treated with a neutral electron donating ligand L other than an N-heterocyclic carbene ligand. ５ It is preferable to carry out the reaction by adding a neutral electron donor ligand L other than an N-heterocyclic carbene ligand to the reaction solution obtained in the first step without carrying out solvent exchange, washing operation, or recrystallization operation. ５ It is preferable to carry out the reaction by adding a ruthenium-containing compound (B) to the catalyst composition obtained in the first step, and therefore it is preferable to use the same solvent as that used in the first step. By employing such a step, the content of the ruthenium-containing compound (B) in the catalyst composition obtained can be suitably controlled within the above-mentioned range.

[0047] In the second step, the neutral electron donor ligand L other than an N-heterocyclic carbene ligand ５ Or such a ligand L ５ The amount of the compound giving the formula (I) is preferably 13 to 30 moles, more preferably 21 to 27 moles, per mole of Ru atom.

[0048] In the second step, the reaction temperature is preferably 10 to 30° C., more preferably 20 to 30° C., and the reaction time is 1 to 3 hours, more preferably 1 to 2 hours.

[0049] Next, in the third step, the reaction solution obtained in the second step is treated with an N-heterocyclic carbene ligand L ６ Or such a ligand L ６ In the third step, the catalyst composition is obtained by adding a compound which gives the formula: ５ One of them is L ６This results in the compound represented by the general formula (8) being produced.

[0050] L ６ is an N-heterocyclic carbene ligand, and as such an N-heterocyclic carbene ligand, those mentioned above can be used.

[0051] In the third step, the reaction mixture obtained in the second step is directly subjected to the addition of an N-heterocyclic carbene ligand L ６ In other words, it is preferable to add the N-heterocyclic carbene ligand L to the reaction solution obtained in the second step without performing solvent exchange, washing, or recrystallization. ６ It is preferable to carry out the reaction by adding a ruthenium-containing compound (B) to the catalyst composition obtained in the second step, and therefore it is preferable to use the same solvent as that used in the second step. By adopting such a step, the content of the ruthenium-containing compound (B) in the catalyst composition obtained can be suitably controlled within the above-mentioned range.

[0052] In the second step, the N-heterocyclic carbene ligand L ６ Or such a ligand L ６ The amount of the compound giving the formula (I) is preferably 10 to 28 moles, more preferably 13 to 21 moles, per mole of Ru atom.

[0053] In the third step, the reaction temperature is preferably 50 to 80° C., more preferably 65 to 75° C., and the reaction time is 5 to 24 hours, more preferably 5.5 to 7 hours.

[0054] In this way, the catalyst composition can be obtained in the form of a catalyst solution dissolved in the solvent used in the reaction. Note that, although the obtained catalyst composition in the form of a catalyst solution may be subjected to an operation for removing the solvent as necessary, it is desirable not to perform a washing operation or a recrystallization operation from the viewpoint of suitably controlling the content ratio of the ruthenium-containing compound (B) in the catalyst composition within the above-mentioned range.

[0055] In addition to the above method, the present invention may also employ a method in which the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) and the ruthenium-containing compound (B) are separately prepared and then mixed to adjust the content ratio thereof within the above range. In this case, the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) may contain, as an unavoidable component, about several mass % of a ruthenium-containing compound (B) other than the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A). Furthermore, the content ratio of the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) to the ruthenium-containing compound (B) may be adjusted by further adding a ruthenium-containing compound (B) to the catalyst composition obtained by the above method.

[0056] <Catalyst Solution> The catalyst solution of the present invention contains the catalyst composition of the present invention described above and a solvent. The solvent is not particularly limited as long as it is inert to the catalyst composition, but examples include aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and trimethylbenzene; ketones such as methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and 4-hydroxy-4-methyl-2-pentanone; cyclic monoethers such as tetrahydrofuran, furan, and 2-methylfuran; cyclic diethers such as 1,3-dioxane, 1,4-dioxane, and 5-methyl-1,3-dioxane; diethyl ether, dichloromethane, dimethyl sulfoxide, and ethyl acetate. Among these, cyclic monoethers are preferred, and tetrahydrofuran is more preferred. The solvents may be used alone or in combination of two or more. The solvent used in producing the catalyst composition may be used as is.

[0057] The content 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 200 parts by mass, more preferably 20 to 167 parts by mass, and even more preferably 33 to 143 parts by mass per part by mass of the total of the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) and the ruthenium-containing compound (B) contained in the catalyst composition.

[0058] <Polymerizable Composition> The polymerizable composition of the present invention is obtained by blending the above-described catalyst composition of the present invention or the catalyst liquid of the present invention with a norbornene-based monomer as a polymerizable monomer.

[0059] 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 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 compounds which are linked to alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, alkylidene groups having 1 to 10 carbon atoms, epoxy groups, or (meth)acrylic groups [CH ２ =CHCH ２ - and / or CH ２ =C(CH ３ ) CH ２ -]. In this specification, the term "(meth)acrylic group" refers to an acrylic group and / or a methacrylic group (hereinafter, the same applies to "(meth)acryloyl group", etc.). The norbornene-based monomers can be used alone or in combination of two or more. As the norbornene-based monomer, the tricyclic rings are preferred, and dicyclopentadiene is particularly preferred, from the viewpoint of further enhancing the effects of the present invention. The norbornene-based monomer used preferably contains 50 mass % or more of the tricyclic rings, especially dicyclopentadiene.

[0060] The content of the norbornene-based monomer in the polymerizable composition of the present invention is not particularly limited, but is preferably 80 to 99.5 mass %, more preferably 85 to 99 mass %, and even more preferably 87 to 98 mass %, relative to 100 mass % of the total polymerizable monomers contained in the polymerizable composition. By setting the content of the norbornene-based monomer within the above range, the strength of the resulting norbornene-based resin can be further increased.

[0061] Furthermore, in the present invention, a monocyclic cycloolefin may be further used as a polymerizable monomer contained in the polymerizable composition. Examples of 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 may be used alone or in combination of two or more.

[0062] The polymerizable composition of the present invention may contain, in addition to the norbornene-based monomer and the monocyclic cycloolefin used as needed, other polymerizable monomers polymerizable with them, such as other cycloolefin monomers and (meth)acrylate-based monomers such as phenoxyethylene glycol (meth)acrylate.

[0063] 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, relative to 100% by mass of the total polymerizable monomers contained in the polymerizable composition, and may be 0% by mass.

[0064] The total content of polymerizable monomers in the polymerizable composition of the present invention is preferably 10 to 95 mass%, more preferably 15 to 93 mass%, and even more preferably 20 to 90 mass%, relative to 100 mass% of the total polymerizable composition.

[0065] The content of the catalyst composition or catalyst solution in the polymerizable composition of the present invention is preferably 50 to 1000 ppm by mass, more preferably 60 to 500 ppm by mass, and even more preferably 70 to 300 ppm by mass, in terms of the catalyst composition, relative to the total amount of polymerizable monomers including cyclic olefin monomers.

[0066] 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, if desired.

[0067] The radical generator generates radicals upon heating, thereby inducing a crosslinking reaction in the norbornene-based resin. The sites at which the radical generator induces the crosslinking reaction are mainly carbon-carbon double bonds contained in the norbornene-based resin, but crosslinking may also occur at saturated bond moieties. Examples of radical generators include organic peroxides, diazo compounds, and non-polar radical generators.

[0068] 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, based on 100 parts by mass of the total amount of polymerizable monomers.

[0069] Examples of diisocyanate compounds 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, tolylene diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, and 4,4'-diisocyanate dibenzidine. Examples of suitable diisocyanate compounds 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, as well as polyurethane prepolymers obtained by reacting these diisocyanate compounds with low-molecular-weight polyols or polyamines so as to form isocyanate groups at the terminals. Furthermore, conventionally known compounds having a polyfunctional isocyanate group, such as isocyanurates, biurets, adducts, or polymers of these compounds, can be used without 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, and polyisocyanate prepolymers.Among these, polyfunctional unblocked isocyanate compounds, such as aromatic diisocyanate compounds, aliphatic diisocyanate compounds, and alicyclic diisocyanate compounds, are preferably used because of their easy availability and ease of handling. These compounds can be used alone or in combination of two or more.

[0070] 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 an alcohol, a phenol, ε-caprolactam, an oxime, or an active methylene compound. Polyfunctional blocked isocyanate compounds generally do not react at room temperature and therefore have excellent storage stability. However, heating at temperatures typically between 140 and 200°C regenerates the isocyanate groups, allowing the compound to exhibit excellent reactivity.

[0071] 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 the polymerizable monomers used in the reaction.

[0072] Furthermore, when norbornene-based resins are combined with other materials, polyfunctional (meth)acrylate compounds may be used to further improve adhesive strength to other materials. By using a polyfunctional (meth)acrylate compound together with a diisocyanate compound, the active hydrogen-reactive group of the diisocyanate compound forms a chemical bond with a hydroxyl group present in the polyfunctional (meth)acrylate compound, which is presumed to further improve 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.

[0073] 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.

[0074] The coupling agent is not particularly limited, but when the norbornene-based resin is combined with other materials, a silane coupling agent having at least one hydrocarbon group having a norbornene structure (norbornene skeleton) is preferred from the viewpoint of improving adhesion to other materials. Specific examples of such silane coupling agents include bicycloheptenyltrimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenylethyltrimethoxysilane, bicycloheptenylethyltriethoxysilane, bicycloheptenylhexyltrimethoxysilane, and bicycloheptenylhexyltriethoxysilane, with bicycloheptenylethyltrimethoxysilane, bicycloheptenylethyltriethoxysilane, bicycloheptenylhexyltrimethoxysilane, and bicycloheptenylhexyltriethoxysilane being preferred, bicycloheptenylethyltrimethoxysilane and bicycloheptenylethyltriethoxysilane being more preferred, and bicycloheptenylethyltrimethoxysilane and bicycloheptenylethyltriethoxysilane being even more preferred, and bicycloheptenylethyltrimethoxysilane being even more preferred.

[0075] 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%.

[0076] 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 a silane coupling agent, such as a thiol coupling agent, an aluminate coupling agent, a titanate coupling agent, or a fatty acid ester.

[0077] Other optional components include an activator, an elastomer, an antioxidant (anti-aging agent), a colorant, a light stabilizer, a flame retardant, and the like.

[0078] The activator is a compound that acts as a cocatalyst for the metathesis polymerization catalyst described above and improves the polymerization activity of the catalyst. Examples of the activator include alkylaluminum halides such as ethylaluminum dichloride and diethylaluminum chloride; alkoxyalkylaluminum halides in which a portion of the alkyl groups in these alkylaluminum halides is substituted with an alkoxy group; and organotin compounds. The amount of the activator used is not particularly limited, but is preferably 0.1 to 100 mol, and more preferably 1 to 10 mol, per mol of the total metathesis polymerization catalysts used in the polymerizable composition.

[0079] Examples of elastomers 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. Dissolving an elastomer in the polymerizable composition allows for adjustment of its viscosity. Furthermore, adding an elastomer can improve the impact resistance of the norbornene-based resin formed by bulk polymerization of the composition. The amount of elastomer used is preferably 0.5 to 20 parts by mass, more preferably 2 to 10 parts by mass, per 100 parts by mass of the total amount of polymerizable monomers in the polymerizable composition.

[0080] Examples of antioxidants (anti-aging agents) include various antioxidants for plastics and rubbers, such as phenol-based, phosphorus-based, and amine-based antioxidants.

[0081] As the colorant, dyes, pigments, etc. are used. There are many types of dyes, and known dyes can be appropriately selected and used. Examples of pigments include carbon black, graphite, yellow lead, iron oxide yellow, titanium dioxide, zinc oxide, trilead tetroxide, red lead, chromium oxide, iron blue, and titanium black.

[0082] Examples of light stabilizers include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, oxanilide-based ultraviolet absorbers, hindered amine-based ultraviolet absorbers, and benzoate-based ultraviolet absorbers.

[0083] 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.

[0084] The polymerizable composition of the present invention may further contain a filler as an optional component. Various fillers can be used as the filler, and although there are no particular limitations, it is preferable to use a particulate inorganic filler.

[0085] The particulate inorganic filler preferably has an aspect ratio of 1 to 2, and more preferably an aspect ratio of 1 to 1.5. The 50% volume cumulative diameter of the particulate 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 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.

[0086] Specific examples of 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. Among these, magnesium hydroxide, aluminum hydroxide, silica, and alumina are preferred, and aluminum hydroxide and silica are particularly preferred.

[0087] The particulate inorganic filler may have its surface hydrophobized. The use of a hydrophobized particulate inorganic filler can prevent aggregation and sedimentation of the particulate inorganic filler in the polymerizable composition and can ensure uniform dispersion of the particulate inorganic filler in the resulting norbornene-based resin. As a result, the strength of the norbornene-based resin can be further increased. Examples of treating agents 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, and the like. The treating agent used for the hydrophobization treatment may be reacted with the particulate inorganic filler in advance to hydrophobize its surface. Alternatively, the treating agent used for the hydrophobization treatment may be incorporated 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.

[0088] The amount of the particulate inorganic filler in the polymerizable composition of the present invention is preferably 10 to 1,000 parts by mass, more preferably 100 to 500 parts by mass, per 100 parts by mass of the total amount of polymerizable monomers.

[0089] 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, more preferably 10 to 50. The 50% cumulative volume diameter of the fibrous inorganic filler is preferably 0.1 to 50 μm, more preferably 1 to 30 μm.

[0090] Specific examples of fibrous inorganic fillers include glass fiber, wollastonite, potassium titanate, zonolite, basic magnesium sulfate, aluminum borate, tetrapod-type zinc oxide, gypsum fiber, phosphate fiber, alumina fiber, whisker-like calcium carbonate, and whisker-like boehmite. Among 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.

[0091] The polymerizable composition of the present invention is prepared by appropriately mixing the above-mentioned components with the above-mentioned catalyst composition or catalyst liquid of the present invention according to a known method. The polymerizable composition of the present invention may also be prepared by preparing the above-mentioned catalyst composition or catalyst liquid of the present invention and one or more other premixed liquids such as a monomer liquid, and mixing the catalyst composition or catalyst liquid with the other premixed liquid such as a monomer liquid using a mixing device or the like just before making into a norbornene-based resin. The catalyst composition or catalyst liquid and the other premixed liquid such as a monomer liquid will not undergo bulk polymerization alone, but are prepared so that when all the liquids are mixed together, a polymerizable composition containing the respective components in predetermined proportions (the total content of each component is 100% by mass).

[0092] Optional components such as a radical generator, a diisocyanate compound, and a polyfunctional (meth)acrylate compound may be contained in either the catalyst composition or catalyst liquid, or another pre-blended liquid such as a monomer liquid, or may be added in the form of a mixed liquid separate from these.

[0093] Examples of mixing devices used to mix the catalyst composition or catalyst liquid with other pre-blended liquids such as a monomer liquid include impingement mixers that are commonly used in reaction injection molding, as well as low-pressure mixers such as dynamic mixers and static mixers.

[0094] <Norbornene-Based Resin> The norbornene-based resin of the present invention is obtained by bulk polymerization of the above-described polymerizable composition of the present invention.

[0095] Examples of methods for producing the norbornene-based resin of the present invention include a method in which the above-mentioned catalyst composition or catalyst solution is directly mixed with another pre-blended solution such as a monomer solution, and a method in which bulk polymerization is carried out in a mold or on a substrate using a mixing device equipped with a mixer or an impingement mixer in which each solution is introduced into a mixing head separately and mixed instantaneously.

[0096] The molding die is not particularly limited, but for example, a mold formed of a male die and a female die can be used. Furthermore, the mold used does not necessarily have to be a highly rigid and expensive mold, and is not limited to a metal mold; a resin mold or a simple mold frame can also be used. When a metal mold is used, the material is not particularly limited, but examples include steel, aluminum, zinc alloy, nickel, copper, chromium, etc., and the metal mold may be manufactured by any method such as casting, forging, thermal spraying, electroforming, etc., or may be plated. The structure of the mold may be determined taking into consideration the pressure when the polymerizable composition is injected into the mold. Furthermore, the clamping pressure of the mold is usually about 0.1 to 9.8 MPa in gauge pressure.

[0097] 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. After the polymerizable composition has stopped flowing through bulk polymerization, the mold is preferably heated to achieve the desired mechanical properties through sufficient polymerization, thereby curing the composition in two stages. The heating temperature is preferably 90 to 200°C, more preferably 100 to 170°C, and even more preferably 110 to 150°C.

[0098] Examples of methods for adjusting the mold temperature include adjusting the mold temperature using a heater; adjusting the temperature of a medium such as cold / hot water or oil circulated through piping embedded inside the mold; and the like.

[0099] After the bulk polymerization is completed, the mold is opened and the resin is removed, thereby obtaining a norbornene-based resin.

[0100] The present invention will be described below based on examples, but the present invention is not limited to these examples. Note that "parts" and "%" are by mass unless otherwise specified.

[0101] Example 1 In a reaction vessel equipped with a condenser and a stirrer, 444 g of tetrahydrofuran was added under an argon atmosphere and heated to 70°C. ３ ) ３ Cl ２ To the mixture, 8.64 g of 1,1-diphenyl-2-propyn-1-ol (diphenylpropargyl alcohol, manufactured by GFS Chemicals) and 2.82 g of 1,1-diphenyl-2-propyn-1-ol were added continuously under stirring, and then 0.5 g of acetyl chloride was added. The mixture was reacted at 70°C for 120 minutes under stirring to obtain a reaction solution.

[0102] Next, the reaction liquid obtained above was cooled to room temperature to a temperature of 25°C, and then 7.83 g of tricyclohexylphosphine was added, and the mixture was reacted at 25°C for 120 minutes with stirring. Thereafter, the mixture was heated again to 70°C, and 6.79 g of 1,3-dimesitylimidazolidin-2-ylidene was added, and the mixture was reacted at 70°C for 6 hours with stirring, thereby obtaining a catalyst liquid containing a catalyst composition.

[0103] The obtained catalyst solution was subjected to quantitative NMR measurement ( １ The content of the compound represented by the following formula (10) in all the ruthenium-containing compounds constituting the catalyst solution was measured by performing H-qNMR, and it was found that the content of the compound represented by the following formula (10) in all the ruthenium-containing compounds was 80 mass %. That is, the catalyst solution of Example 1 contained, as a catalyst composition, "a compound represented by the following formula (10) as an N-heterocyclic carbene ligand-containing ruthenium carbene complex (A):a ruthenium-containing compound (B) other than the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A)" in a mass ratio of 80:20. Furthermore, the obtained catalyst solution was subjected to quantitative NMR measurement ( １When H-qNMR was performed, it was confirmed that the catalyst solution contained, as the ruthenium-containing compound (B), a compound represented by the following formula (11) and ruthenium oxide.

[0104] In addition, quantitative NMR measurement ( １ H-qNMR) was performed under the following conditions: NMR apparatus: JNM-ECZL400S, manufactured by JEOL Ltd. Observation center and width: δ 5 ppm ± 5 ppm Acquisition time: 5 seconds Pulse angle: 45° Delay time: 5 seconds Number of integrations: 8 Measurement temperature: 25°C Dummy scan: 0 Spinning: Off １３ C decoupling: On Standard sample: 1,4-BTMSB-d4 Solvent: deuterated benzene

[0105] Example 2 A catalyst solution was prepared in the same manner as in Example 1, except that the reaction time during the reaction by stirring after adding 1,3-dimesitylimidazolidin-2-ylidene in Example 1 was changed from 6 hours to 5 hours. The obtained catalyst solution was then subjected to quantitative NMR measurement ( １ As a result of performing quantitative NMR (H-qNMR), it was found that the catalyst solution of Example 2 contained, as a catalyst composition, "a compound represented by the following formula (10) as a ruthenium carbene complex (A) containing an N-heterocyclic carbene ligand:a ruthenium-containing compound (B) other than the ruthenium carbene complex (A) containing an N-heterocyclic carbene ligand" in a mass ratio of 60:40. １ When H-qNMR was performed, it was confirmed that the catalyst solution contained the compound represented by the above formula (11) and ruthenium oxide as the ruthenium-containing compound (B).

[0106] Comparative Example 1 0.1 g of commercially available (3-phenyl-1H-inden-1-ylidene) (1,3-dimesitylimidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium (IV) dichloride (manufactured by Umicore) was prepared and dissolved in 33.23 g of cyclopentanone to obtain a catalyst solution. The obtained catalyst solution was then subjected to quantitative NMR measurement ( １ As a result of performing H-qNMR, it was found that the catalyst solution of Example 2 contained, as a catalyst composition, "a compound represented by the following formula (10) as an N-heterocyclic carbene ligand-containing ruthenium carbene complex (A):a ruthenium-containing compound (B) other than the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A)" in a mass ratio of 93:7.

[0107] Example 3: RIM monomer (manufactured by Zeon Corporation) was used as the monomer liquid, and the catalyst liquid obtained in Example 1 was added to the RIM monomer in an amount of 100 ppm, calculated as the compound represented by formula (10), and mixed in a glass container to form a polymerizable composition, and the curing time of the polymerizable composition was measured. The curing time was measured as the time until the viscosity reached 400 mPa s, and this was taken as the curing time. The results are shown in Table 1. The composition of the RIM monomer was approximately 90 parts dicyclopentadiene and approximately 10 parts tricyclopentadiene.

[0108] A mold made of aluminum 5052 and having inner dimensions of 300 mm in length, 250 mm in width, and 4 mm in depth and treated with a release agent was prepared and covered with an aluminum 5052 flat plate. The mold was then set to 30°C, and the polymerizable composition prepared by the method described above was poured into the mold until it was fully filled. After leaving the mold for 1 hour, the mold was heated to 60°C and allowed to stand for another 1 hour, at which point the polymerizable composition no longer flowed within the mold. The mold was then heated to 120°C and allowed to stand for 1 hour. The mold was then cooled to room temperature and demolded to obtain a norbornene-based resin molded article. The resulting norbornene-based resin molded article was used to measure its DSC curve from 30°C to 220°C at a heating rate of 10°C / min using a differential scanning calorimeter (DSC-6220, manufactured by Seiko Instruments Inc.). The glass transition temperature (Tg) was measured by reading the intersection of a line extending the baseline on the lower temperature side of the inflection point and a line extending the baseline on the higher temperature side of the inflection point from the DSC curve obtained. The results are shown in Table 1.

[0109] Example 4 A polymerizable composition and a norbornene-based resin molded product were obtained in the same manner as in Example 3, except that the catalyst solution obtained in Example 2 was used in an amount of 100 ppm, calculated as the compound represented by formula (10), relative to the RIM monomer, and the curing time and glass transition temperature (Tg) were measured in the same manner as in Example 3. The results are shown in Table 1.

[0110] Comparative Example 2 A polymerizable composition and a norbornene-based resin molded product were obtained in the same manner as in Example 3, except that the catalyst solution obtained in Comparative Example 1 was used in an amount of 100 ppm, calculated as the compound represented by formula (10), relative to the RIM monomer, and the curing time and glass transition temperature (Tg) were measured in the same manner as in Example 3. The results are shown in Table 1.

[0111] Examples 5 and 6, Comparative Example 3 Polymerizable compositions and norbornene-based resin molded articles were obtained in the same manner as in Examples 3 and 4 and Comparative Example 2, respectively, except that the amount of catalyst solution used was 200 ppm in terms of the compound represented by formula (10), and the curing time and glass transition temperature (Tg) were measured in the same manner. The results are shown in Table 1.

[0112] Examples 7 and 8, Comparative Example 4 Polymerizable compositions and norbornene-based resin molded articles were obtained in the same manner as in Examples 3 and 4 and Comparative Example 2, respectively, except that the amount of catalyst solution used was 300 ppm in terms of the compound represented by formula (10), and the curing time and glass transition temperature (Tg) were measured in the same manner. The results are shown in Table 1.

[0113]

[0114] The results in Table 1 confirm that a catalyst composition containing an N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) and a ruthenium-containing compound other than the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) (B) in a mass ratio of N-heterocyclic carbene ligand-containing ruthenium carbene complex (A):ruthenium-containing compound (B) in the range of 50:50 to 90:10 has a long curing time and therefore a long usable time, and further the glass transition temperature of the obtained molded article is sufficiently high and has excellent catalytic activity.

Claims

1. A catalyst composition comprising an N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) represented by the following general formula (1) or (2), and a ruthenium-containing compound (B) other than the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A), wherein the mass ratio of the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) to the ruthenium-containing compound (B) is N-heterocyclic carbene ligand-containing ruthenium carbene complex (A):ruthenium-containing compound (B) = 50:50 to 90:

10. (In the above general formulas (1) and (2), 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; and these groups may have a substituent, and may also be bonded to each other to form a ring. １ and X ２ are each independently any anionic ligand. １ and L ２ is an N-heterocyclic carbene ligand or a neutral electron donor ligand other than an N-heterocyclic carbene ligand, and L １ and L ２ At least one of is an N-heterocyclic carbene ligand.

2. The catalyst composition according to claim 1, wherein the N-heterocyclic carbene ligand is a compound represented by the following general formula (3) or (4): (In the above general formulas (3) and (4), 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.

3. In the general formula (1) and the general formula (2), L １ is a compound represented by the general formula (3) or (4), and L ２ The catalyst composition according to claim 2, wherein is a phosphine.

4. The catalyst composition according to any one of claims 1 to 3, wherein the N-heterocyclic carbene ligand-containing ruthenium carbene complex (A) is a compound represented by the following general formula (5): (In the above general formula (5), PCy ３ represents tricyclohexylphosphine, Mes represents a mesityl group, and R ９ , R １０ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

5. The catalyst composition according to any one of claims 1 to 4, wherein the ruthenium-containing compound (B) is at least a compound represented by the following general formula (6) or (7): (In the above general formulas (6) and (7), R １１ and R １２ 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 also be bonded to each other to form a ring. ３ and X ４ are each independently any anionic ligand. ３ and L ４ is a neutral electron donating ligand other than an N-heterocyclic carbene ligand.

6. A catalyst liquid comprising the catalyst composition according to any one of claims 1 to 5 and a solvent.

7. A polymerizable composition obtained by blending the catalyst composition according to any one of claims 1 to 5 or the catalyst liquid according to claim 6 with a norbornene-based monomer as a polymerizable monomer.

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