Catalyst liquid and method for producing catalyst liquid

Abstract

The present invention provides a catalyst liquid containing a metal oxo complex represented by general formula (1), and further containing MoOCl4 and / or WOCl4, the total content of MoOCl4 and WOCl4 being 0.5-20 parts by weight per 100 parts by weight of the metal oxo complex. [In general formula (1), M represents a molybdenum atom or a tungsten atom, A represents a carbon atom, a silicon atom, a germanium atom, a tin atom, or a lead atom, R1-R5 each independently represent a hydrogen atom, an optionally substituted linear or branched alkyl group having 1-20 carbon atoms, or an optionally substituted aryl group having 6-20 carbon atoms, and R1-R3 may each bond to each other to form a ring. ]

Description

Technical Field

[0001] This invention relates to catalyst liquids and methods for manufacturing catalyst liquids, and more specifically, to catalyst liquids capable of forming polymeric compositions with excellent release properties and filler properties, and methods for manufacturing such catalyst liquids. Background Technology

[0002] Transition metal carbene complexes, such as ruthenium carbene complexes known as Grubb catalysts, molybdenum carbene complexes known as Schrock catalysts, and tungsten carbene complexes, are known and widely used as highly active catalysts for metathesis reactions (hereinafter, sometimes referred to as "metathesis catalysts").

[0003] Among transition metal carbene complexes, molybdenum carbene complexes and tungsten carbene complexes exhibit extremely high activity as metathesis catalysts. Furthermore, as disclosed in Patent Document 1, by appropriately selecting the substituents and ligands on the metal, they can perform metathesis reactions with stereospecificity. Therefore, various studies have been conducted on molybdenum carbene complexes and tungsten carbene complexes.

[0004] For example, Patent Document 1 discloses a metal oxo complex that is coordinated with molybdenum or tungsten atoms by -OA(R 1 R 2 R 3 The group represented by ) (A represents a carbon atom, silicon atom, germanium atom, tin atom, or lead atom, R) 1 ~R 3 Each can independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms that can have substituents (either straight or branched), or an aryl group with 6 to 20 carbon atoms that can have substituents, R 1 ~R 3 They can bond together to form rings. ) and β-diketone are obtained. In the technology of this patent document 1, when obtaining the metal oxo complex, it is separated by a recrystallization process, and the separated metal oxo complex is dissolved in a solvent to obtain a catalyst solution.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent document 1: International Publication No. 2020 / 085306. Summary of the Invention

[0008] The problem the invention aims to solve

[0009] However, in the technology of the aforementioned Patent Document 1, the release property is insufficient when manufacturing polymeric compositions, therefore, from the point of view of productivity, improvement is desired.

[0010] The present invention was made in view of the following actual situation, and its object is to provide a catalyst liquid capable of forming polymeric compositions with excellent release properties and filling properties.

[0011] means for solving problems

[0012] The inventors conducted research to achieve the above-mentioned objective and discovered that the objective can be achieved by using a catalyst liquid in which -OA(R) is coordinated to molybdenum or tungsten atoms. 1 R 2 R 3 The group represented by ) (A represents a carbon atom, silicon atom, germanium atom, tin atom, or lead atom, R) 1 ~R 3 Each can independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms that can have substituents (either straight or branched), or an aryl group with 6 to 20 carbon atoms that can have substituents, R 1 ~R 3 The invention comprises a metal-oxometalate complex consisting of β-diketones and β-diones, containing specific amounts of MoOCl4 and / or WOCl4.

[0013] That is, according to the present invention, the following invention is provided.

[0014] [1] A catalyst liquid containing a metal oxo complex represented by the following general formula (1), and also containing MoOCl4 and / or WOCl4, wherein the total content of MoOCl4 and WOCl4 is 0.5 to 20 parts by weight relative to 100 parts by weight of the above metal oxo complex.

[0015] [Chemistry 1]

[0016]

[0017] In the above general formula (1), M represents a molybdenum atom or a tungsten atom, A represents a carbon atom, a silicon atom, a germanium atom, a tin atom, or a lead atom, and R represents a carbon atom, silicon atom, germanium atom, tin atom, or lead atom. 1 ~R 5 Each can independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms that can have substituents (either straight or branched), or an aryl group with 6 to 20 carbon atoms that can have substituents, R 1 ~R 3 They can bond together to form rings.

[0018] [2] The catalyst liquid according to [1] also contains norbornene monomers.

[0019] [3] The catalyst liquid according to [1] or [2], wherein A is a carbon atom or a silicon atom in the above general formula (1).

[0020] [4] The catalyst liquid according to any one of [1] to [3], wherein, in the above general formula (1), R 4 and R 5 At least one of them is methyl or tert-butyl.

[0021] [5] The catalyst liquid according to any one of [1] to [4], wherein, in the above general formula (1), R 1 R 2 It consists of alkyl groups with 1 to 20 carbon atoms that are straight or branched and can have substituents, and which are bonded together to form a ring.

[0022] [6] A method for manufacturing a catalyst liquid, comprising the method of manufacturing the catalyst liquid described in any one of [1] to [5], comprising:

[0023] The first step involves reacting MoCl6 and / or WCl6 with a ketone compound in an aliphatic solvent to obtain a solution containing MoOCl4 and / or WOCl4.

[0024] The second step involves reacting a compound represented by the following general formula (2) with a solution containing MoOCl4 and / or WOCl4 obtained in the first step above, thereby obtaining a solution containing a compound represented by the following general formula (3); and

[0025] In the third step, the compound represented by the following general formula (4) is reacted with the solution containing the compound represented by the general formula (3) obtained in the second step above, thereby obtaining a catalyst solution containing the metal oxo complex represented by the above general formula (1) and also containing MoOCl4 and / or WOCl4.

[0026] [Chemistry 2]

[0027]

[0028] In the above general formulas (2) to (4), A represents a carbon atom, silicon atom, germanium atom, tin atom, or lead atom, and R... 1 ~R 5 Each can independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms that can have substituents (either straight or branched), or an aryl group with 6 to 20 carbon atoms that can have substituents, R 1 ~R 3 They can bond together to form rings.

[0029] The effects of the invention

[0030] According to the present invention, a catalyst liquid capable of forming a polymerizable composition with excellent release and filling properties can be provided, as well as a method for obtaining such a catalyst liquid. Attached Figure Description

[0031] Figure 1 This is a graph showing the results of NMR measurements in Example 1. Detailed Implementation

[0032] <Catalyst solution>

[0033] The catalyst liquid of the present invention contains a metal oxo complex represented by the following general formula (1), and also contains MoOCl4 and / or WOCl4.

[0034] [Chemistry 3]

[0035]

[0036] In the above general formula (1), M represents a molybdenum atom or a tungsten atom, A represents a carbon atom, a silicon atom, a germanium atom, a tin atom, or a lead atom, and R... 1 ~R 5 Each can independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms that can have substituents (either straight or branched), or an aryl group with 6 to 20 carbon atoms that can have substituents, R 1 ~R 3 They can bond with each other to form a ring.

[0037] In the above general formula (1), M represents a molybdenum atom or a tungsten atom as the central metal of the complex. The central metal of the metal oxo-complex used in this invention can be either a molybdenum atom or a tungsten atom, but from the viewpoint of superior catalyst activity, a tungsten atom is preferred.

[0038] Furthermore, the compounds represented by the above general formula (1) have the following characteristics: -OA(R 1 R 2 R 3 The group represented by ) serves as the ligand. It is presumed that the metal oxo complex used in this invention has a group consisting of -OA(R) groups. 1 R 2 R 3 The structure, represented by the group and coordinated with a β-diketone, exhibits excellent stability in air. Therefore, the metal oxo complexes used in this invention possess excellent handling properties.

[0039] In the above general formula (1), A represents a carbon atom, a silicon atom, a germanium atom, a tin atom, or a lead atom. From the viewpoint of being able to further improve the stability of the metal oxo complex in air, a carbon atom or a silicon atom is preferred, and a carbon atom is more preferred.

[0040] Furthermore, it constitutes -OA(R) 1 R 2 R 3 The R group represented by ) 1 ~R3 Each can independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms that can have substituents (either straight or branched), or an aryl group with 6 to 20 carbon atoms that can have substituents. Furthermore, R... 1 ~R 3 They are capable of bonding with each other to form a ring. Specific examples of alkyl groups with 1 to 20 carbon atoms that can have substituents, whether straight or branched, are not particularly limited, but include methyl, ethyl, isopropyl, tert-butyl, n-butyl, 2,2-dimethylpropyl, 2-methyl-2-phenylethyl, etc. Specific examples of aryl groups with 6 to 20 carbon atoms that can have substituents are not particularly limited, but include phenyl, 4-methylphenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, mesitylene, etc. 1 ~R 3 The groups represented can be the same group or different groups.

[0041] In addition, R 1 ~R 3 They can bond together to form a ring, in which case, as a component of -OA(R) 1 R 2 R 3 The group represented by -A(R) 1 R 2 R 3 Specific examples of the group represented by (where A is a carbon atom) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, norbornyl, bornyl, isobornyl, decahydronaphthyl, tricyclodecyl, adamantyl, etc. These groups can have substituents, among which cyclohexyl with substituents is preferred. Examples of such substituents include methyl, ethyl, isopropyl, tert-butyl, n-butyl, 2,2-dimethylpropyl, phenyl, etc., among which methyl and isopropyl are preferred.

[0042] In the compounds represented by the above general formula (1), R 4 R 5 It is a group that bonds to the β-diketone structure as a ligand, R 4 R 5Each can independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms (either straight-chain or branched) capable of having substituents, or an aryl group with 6 to 20 carbon atoms capable of having substituents. Specific examples of alkyl groups with 1 to 20 carbon atoms (either straight-chain or branched) capable of having substituents are not particularly limited, but may include methyl, ethyl, isopropyl, tert-butyl, n-butyl, 2,2-dimethylpropyl, 2-methyl-2-phenylethyl, etc. Specific examples of aryl groups with 6 to 20 carbon atoms capable of having substituents are not particularly limited, but may include phenyl, 4-methylphenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, mesitylene, etc. (The last part, "R," appears to be a typo and can be left as is.) 4 R 5 The groups represented can be the same groups or different groups.

[0043] In the metal oxo complexes used in this invention, from the viewpoint of further improving the solubility of the monomers used to obtain the polymer, R is preferred. 4 R 5 At least one of them is methyl or tert-butyl. In particular, from the viewpoint of being able to further improve the solubility of the monomers used to obtain the polymer, R is more preferred. 4 R 5 Both are methyl, or R 4 R 5 Both are tert-butyl.

[0044] In the metal oxo complexes of the present invention, among the compounds represented by the above general formula (1), compounds represented by formulas (5) to (15) are preferred, compounds represented by formulas (5), (7), (8), (9), (10), (11), (14), and (15) are more preferred, compounds represented by formulas (14) and (15) are even more preferred, and compounds represented by formula (15) are particularly preferred.

[0045] [Chemistry 4]

[0046]

[0047] In addition to the metal oxometalate complex represented by the above general formula (1), the catalyst solution of the present invention also contains MoOCl4 and / or WOCl4. In the catalyst solution of the present invention, the content of MoOCl4 and / or WOCl4 is 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, and more preferably 2.5 to 12 parts by weight, relative to 100 parts by weight of the metal oxometalate complex represented by the above general formula (1), based on the total content of MoOCl4 and WOCl4.

[0048] According to the present invention, by containing the specific amounts of MoOCl4 and / or WOCl4 relative to the metal oxide complex represented by the above general formula (1) and using it as a catalyst liquid, in addition to the excellent stability in air possessed by the metal oxide complex represented by the above general formula (1), excellent release properties and fillability are also observed when incorporated into a polymerizable composition. If the total content of MoOCl4 and WOCl4 is too low, the release properties become insufficient; if the total content of MoOCl4 and WOCl4 is too high, the catalyst activity decreases.

[0049] It should be noted that the catalyst liquid of the present invention may contain either MoOCl4 or WOCl4, or both. In the case where the M atom of the metal oxo complex represented by the above general formula (1) is a molybdenum atom, it is preferable to contain MoOCl4. In the case where the M atom of the metal oxo complex represented by the above general formula (1) is a tungsten atom, it is preferable to contain WOCl4.

[0050] Furthermore, as for the method of containing the specific amount of MoOCl4 and / or WOCl4 relative to the metal oxo complex represented by the above general formula (1), there is no particular limitation. Method (A) can be adopted: by synthesizing and separating the metal oxo complex represented by the above general formula (1), and mixing MoOCl4 and / or WOCl4 in the separated metal oxo complex represented by the above general formula (1); or, method (B) can be adopted: as in the method for manufacturing the catalyst liquid of the present invention described below, when synthesizing the metal oxo complex represented by the above general formula (1), the MoOCl4 and / or WOCl4 generated during the synthesis process are left as a residue, thereby serving as a substance containing the metal oxo complex represented by the above general formula (1) and containing MoOCl4 and / or WOCl4.

[0051] <Method for manufacturing catalyst solution>

[0052] Hereinafter, the method for manufacturing the catalyst liquid of the present invention, which is the method for manufacturing the catalyst liquid of the above method (B), will be described.

[0053] The method for manufacturing the catalyst liquid of the present invention includes:

[0054] The first step involves reacting MoCl6 and / or WCl6 with a ketone compound in an aliphatic solvent to obtain a solution containing MoOCl4 and / or WOCl4.

[0055] The second step involves reacting a compound represented by the following general formula (2) with a solution containing MoOCl4 and / or WOCl4 obtained in the first step above, thereby obtaining a solution containing a compound represented by the following general formula (3); and

[0056] In the third step, the compound represented by the following general formula (4) is reacted with the solution containing the compound represented by the general formula (3) obtained in the second step above, thereby obtaining a catalyst solution containing the metal oxo complex represented by the above general formula (1) and also containing MoOCl4 and / or WOCl4.

[0057] [Chemistry 5]

[0058]

[0059] (First process)

[0060] First, in the first step, MoCl6 and / or WCl6 are reacted with ketone compounds (monoketone compounds) in an aliphatic solvent to obtain a solution containing MoOCl4 and / or WOCl4.

[0061] As an aliphatic solvent, there are no particular limitations; any solvent that does not hinder the reaction is acceptable. Examples include propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, propylene, 1-butene, isobutene, trans-2-butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, n-heptane, and other straight-chain or branched aliphatic hydrocarbons; cyclopentane, cyclohexane, and other alicyclic hydrocarbons; and ether compounds such as tetrahydrofuran and diethyl ether. Among these, straight-chain or branched aliphatic hydrocarbons are preferred, and n-hexane is more preferred.

[0062] The term "ketone compound" (monoketone compound) is not particularly limited, and examples include acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, methyl isobutyl ketone, methyl hexyl ketone, diisobutyl ketone, butyraldehyde, propyl acetate, butyl acetate, and amyl acetate. Among these, acetone is preferred.

[0063] In the first step, when reacting MoCl6 and / or WCl6 with the ketone compound, methods such as mixing them in an aliphatic solvent can be used. The reaction temperature is not particularly limited, but is preferably 0–100°C, more preferably 25–65°C. The reaction time is not particularly limited, but is preferably 1–48 hours, more preferably 2–24 hours. Furthermore, an inert gas atmosphere is preferred as the reaction atmosphere.

[0064] Furthermore, the amount of MoCl6 and / or WCl6 and the ketone compound used in the first step is not particularly limited, but is preferably 1:1 to 1:1.05, more preferably 1:1 to 1:1.03, and even more preferably 1:1 to 1:1.01, based on the ratio of "total molar amount of MoCl6 and WCl6 to molar amount of ketone compound".

[0065] (Second process)

[0066] In the second step, the compound represented by the following general formula (2) is reacted with the solution containing MoOCl4 and / or WOCl4 obtained in the first step above, thereby obtaining a solution containing the compound represented by the following general formula (3).

[0067] [Chemistry 6]

[0068]

[0069] In the above general formulas (2) and (3), R 4 R 5 Each of the following can be represented independently as a hydrogen atom, an alkyl group with 1 to 20 carbon atoms that can have a substituent in a straight or branched chain, or an aryl group with 6 to 20 carbon atoms that can have a substituent, as specific examples of the same general formula (1) above.

[0070] In the second step, the method for reacting the compound represented by the above general formula (2) with the solution containing MoOCl4 and / or WOCl4 obtained in the first step is not particularly limited. Examples include adding the compound represented by the above general formula (2) to the solution containing MoOCl4 and / or WOCl4 obtained in the first step and mixing them. The reaction temperature is not particularly limited, but is preferably 0 to 100°C, more preferably 25 to 65°C. The reaction time is not particularly limited, but is preferably 1 to 48 hours, more preferably 2 to 24 hours. Furthermore, an inert gas atmosphere is preferred as the reaction atmosphere.

[0071] It should be noted that in the second step, MoOCl4 and / or WOCl4 are reacted with the compound represented by the above general formula (2). In the manufacturing method of the present invention, in this second step, the amount of MoOCl4 and / or WOCl4 remaining in the MoOCl4 and / or WOCl4 that has not reacted with the compound represented by the above general formula (2) becomes the amount of MoOCl4 and / or WOCl4 in the final catalyst solution.

[0072] Therefore, in the second step, the amount of compound represented by the above general formula (2) added relative to the amount of MoOCl4 and / or WOCl4 can be determined based on the reaction rate of MoOCl4 and / or WOCl4 with the compound represented by the above general formula (2) so that the amount of MoOCl4 and / or WOCl4 in the final catalyst solution is the desired amount. It is preferably 1:1 to 1:1.05, more preferably 1:1 to 1:1.03, and even more preferably 1:1 to 1:1.01, based on the ratio of "molar amount of MoOCl4 and / or WOCl4 contained in the solution containing MoOCl4 and / or WOCl4 obtained in the first step to molar amount of the compound represented by the above general formula (2)".

[0073] (Third process)

[0074] In the third step, the compound represented by the following general formula (4) is reacted with the solution containing the compound represented by the general formula (3) obtained in the second step above, thereby obtaining a catalyst solution containing the metal oxo complex represented by the above general formula (1) and also containing MoOCl4 and / or WOCl4.

[0075] [Chemistry 7]

[0076]

[0077] In the above general formula (4), A represents a carbon atom, silicon atom, germanium atom, tin atom, or lead atom, and R... 1 ~R 3 Each can independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms that can have substituents (either straight or branched), or an aryl group with 6 to 20 carbon atoms that can have substituents, R 1 ~R 3 They can bond with each other to form a ring. In the above general formula (4), A and R 1 ~R 3 The specific examples are the same as those in the general formula (1) above.

[0078] In the third step, the method for reacting the compound represented by the above general formula (4) with the solution containing the compound represented by ...

[0079] Furthermore, the amount of the compound represented by the above general formula (4) used in the third step is not particularly limited, but is preferably 1:1 to 1:1.05, more preferably 1:1 to 1:1.03, and even more preferably 1:1 to 1:1.01, based on the ratio of "molar amount of the compound represented by the above general formula (3) obtained in the second step to molar amount of the compound represented by the above general formula (4)".

[0080] Furthermore, in the manufacturing method of the present invention, for the solution obtained in the third step containing the metal oxo complex represented by the above general formula (1) and also containing MoOCl4 and / or WOCl4, volatile components such as aliphatic solvents are distilled off as needed, thereby obtaining the catalyst liquid of the present invention. In addition, the solvent may be cleaned as needed.

[0081] According to the manufacturing method of the present invention, there is no need for a step of separating the metal oxo complex represented by the above general formula (1) by recrystallization or the like. Furthermore, by controlling the amount of the compound represented by the above general formula (2) used to react with MoOCl4 and / or WOCl4 in the second step, the amount of MoOCl4 and / or WOCl4 in the final catalyst liquid can be appropriately controlled within the above range. Thus, without the need for separation steps such as recrystallization, a catalyst liquid capable of forming a polymeric composition with excellent release properties and filling properties can be obtained with high production efficiency.

[0082] However, in this invention, any method capable of producing the catalyst liquid of this invention may be used other than the method described above. For example, for the solution obtained in the third step above that contains the metal oxo complex represented by the general formula (1) and also contains MoOCl4 and / or WOCl4, the following steps may be used: after distilling off volatile components such as aliphatic solvents, recrystallization is performed to separate the metal oxo complex represented by the general formula (1), and then MoOCl4 and / or WOCl4 are added and mixed.

[0083] <Application as a precursor to metathesis catalysts>

[0084] The catalyst liquid of the present invention is suitable as a precursor for metathesis catalysts because it contains a metal oxo complex represented by the above general formula (1).

[0085] When the catalyst liquid of the present invention is used as a precursor for a metathesis catalyst, it is typically activated by contacting it with an organometallic compound commonly used in metathesis polymerization catalysts, and then used in the activated state for metathesis polymerization reactions. That is, by contacting the metal oxo complex represented by the above general formula (1) contained in the catalyst liquid of the present invention with an organometallic compound, the metal oxo complex represented by the above general formula (1) can react with the organometallic compound, thereby making the catalyst liquid of the present invention a metathesis polymerization catalyst. At this time, since the catalyst liquid of the present invention contains the above-described specified amounts of MoOCl4 and / or WOCl4, through the action of MoOCl4 and / or WOCl4, when further containing polymerizable monomers to become a polymerizable composition, it can possess excellent release properties and filling properties.

[0086] Organometallic compounds used as activators can include, for example, organometallic compounds of metals from Groups 11 to 14 of the periodic table. Specific examples include: alkylaluminum compounds such as triethylaluminum, triisobutylaluminum, trimethylaluminum, tributylaluminum, trihexylaluminum, and trioctylaluminum; alkylaluminum halide compounds such as ethylaluminum dichloride, diethylaluminum chloride, diisobutylaluminum chloride, ethyl sesquichloride, isobutylaluminum dichloride, and dioctylaluminum iodide; alkylalkoxyaluminum compounds such as diethylethoxyaluminum; organotin compounds such as tetrabutyltin; organozinc compounds such as diethylzinc; and organomagnesium compounds such as isopropylmagnesium chloride. Among these, alkylaluminum compounds and alkylaluminum halide compounds are preferred, triethylaluminum, trioctylaluminum, diethylaluminum chloride, and dioctylaluminum iodide are more preferred, and triethylaluminum and diethylaluminum chloride are even more preferred. One organometallic compound can be used as an activator, or two or more can be used in combination.

[0087] When the catalyst liquid of the present invention is used as a precursor for metathesis catalyst, norbornene monomers can be suitably used as polymerizable monomers.

[0088] In this case, it is preferable to pre-contain norbornene monomers in the catalyst solution of the present invention. That is, it is preferable to contain a metal oxometalate complex represented by the above general formula (1), MoOCl4 and / or WOCl4, and norbornene monomers in the catalyst solution of the present invention. The content of norbornene monomers in the catalyst solution of the present invention is preferably 100 to 2000 parts by weight relative to 100 parts by weight of the metal oxometalate complex represented by the above general formula (1), more preferably 400 to 1600 parts by weight, and even more preferably 700 to 1200 parts by weight. By setting the content of norbornene monomers within the above range, the viscosity of the catalyst solution of the present invention can be kept within an appropriate range, thereby improving operability and productivity.

[0089] As a norbornene monomer, any compound having a norbornene structure is acceptable; there are no particular limitations. Specific examples include:

[0090] Dicyclopentadiene, methyldicyclopentadiene, and other dicyclopentadiene derivatives;

[0091] Fourth Ring Road [6.2.1.1] 3,6 .0 2,7 [6.2.1.1 Dodecyl-4-ene, 9-ethylidene tetracyclo[6.2.1.1] 3,6 .0 2,7 [6.2.1.1] Dodecyl-4-ene, 9-phenyltetracyclo[6.2.1.1] 3,6 .0 2,7 [Dodecyl-4-ene, tetracyclo[6.2.1.1]] 3,6 .0 2,7[Docodecano-9-ene-4-carboxylic acid, tetracyclic [6.2.1.1]] 3,6 .0 2,7 Tetracyclic dodecenes, such as dodecene-9-ene-4,5-dicarboxylic anhydride;

[0092] 2-Norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-phenyl-2-norbornene, 5-norbornene-2-yl acrylate, 5-norbornene-2-yl methacrylate, 5-norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic anhydride, and other norbornene derivatives;

[0093] 7-Oxa-2-norbornene, 5-ethylidene-7-oxa-2-norbornene, and other oxa-norbornene derivatives;

[0094] Fourth Ring Road [9.2.1.0] 2,10 .0 3,8 [Tetradecane-3,5,7,12-tetraene (also known as 1,4-bridged methylene-1,4,4a,9a-tetrahydro-9H-fluorene), pentacyclic [6.5.1.1] 3,6 .0 2,7 .0 9,13 [Pentadecano-4,10-diene, pentacyclic [9.2.1.0]] 2,10 .0 3,8 Cyclic alkenes with four or more rings, such as pentadecyl-5,12-diene and tricyclopentadiene.

[0095] Metathesis polymerization reactions using the catalyst liquid of the present invention can be carried out in a solvent or under solvent-free conditions. For example, by containing the metal oxo complex represented by the above general formula (1), MoOCl4 and / or WOCl4, and norbornene monomers in the catalyst liquid of the present invention, polymerization reactions under solvent-free conditions such as bulk polymerization can be achieved.

[0096] Example

[0097] The present invention will now be described based on embodiments, but the invention is not limited to these embodiments in any way. Additionally, "parts" and "%" are used as mass units unless otherwise specified.

[0098] <Example 1>

[0099] (Preparation of catalyst solution)

[0100] In a reaction vessel equipped with a stirrer, under a nitrogen atmosphere, 488.79 g of hexane and 140 g (353.05 mmol) of tungsten chloride (VI)(WCl6) were added, and the mixture was stirred for 1 hour. Next, the temperature of the reaction vessel was adjusted to 55°C, and under a nitrogen atmosphere, 41.01 g (353.05 mmol) of acetone was added continuously over 27 minutes. After the acetone addition was complete, the temperature of the reaction vessel was maintained at 55°C, and the mixture was stirred for 5 hours. Then, while maintaining the temperature of the reaction vessel at 55°C, under a nitrogen atmosphere, 70.70 g (353.05 mmol) of acetylacetone was added continuously over 32 minutes. After the acetylacetone addition was complete, the temperature of the reaction vessel was maintained at 55°C, and the mixture was stirred for 18 hours. Next, under a nitrogen atmosphere, 110.34 g (353.05 mmol) of L-menthol (2-isopropyl-5-methylcyclohexanol) was added continuously over 36 minutes. After the addition of L-menthol was completed, the temperature of the reaction vessel was maintained at 55 °C, and the mixture was stirred for 26 hours. The resulting reaction solution was then distilled to remove volatile components containing hexane, yielding a yellowish-brown viscous substance.

[0101] Then, using a portion of the obtained viscous substance, a hexane suspension was prepared by adding hexane. The hexane suspension was then centrifuged to precipitate the insoluble matter. The yellowish-brown solution of the supernatant was collected and left to stand at room temperature overnight to obtain yellowish-brown needle-like crystals. Then, based on NMR measurements, it was confirmed that the obtained needle-like crystals were the compound represented by formula (15). The NMR results are shown in... Figure 1 .

[0102] [Chemistry 8]

[0103]

[0104] In addition, the obtained yellowish-brown viscous substance was subjected to... 183 The results of W-NMR analysis showed that the content of WOCl4 in the viscous substance was 8.4 parts per 100 parts of the compound represented by formula (15).

[0105] Next, relative to 0.83 parts of the compound represented by formula (15) in the obtained yellowish-brown viscous substance, 99.17 parts of a mixture of norbornene monomers (RIM-M) consisting of 90% dicyclopentadiene and 10% tricyclopentadiene were added to obtain a catalyst solution. After stirring the obtained catalyst solution for 10 minutes, the viscosity of the catalyst solution was measured using a type B viscometer, and the result was 2900 mPa·s.

[0106] (Preparation of activator solution A)

[0107] In a reaction vessel, under a nitrogen atmosphere, triethylaluminum was added to dipropylene glycol dimethyl ether and mixed to dissolve it in a mixture of norbornene monomers (RIM-M) consisting of 90% dicyclopentadiene and 10% tricyclopentadiene, so that the concentration of triethylaluminum was 0.13%, to obtain activator solution A.

[0108] (Preparation of reaction stock solution B)

[0109] In a reaction vessel, under a nitrogen atmosphere, the catalyst solution obtained above was added to a mixture of norbornene monomers (RIM-M) consisting of 90% dicyclopentadiene and 10% tricyclopentadiene, such that the amount of tungsten was 3.5 mmol / kg, and the mixture was stirred to obtain reaction stock solution B. Furthermore, when preparing reaction stock solution B, the catalyst solution obtained above was stored under a nitrogen atmosphere for 3 days before use.

[0110] (Polymer manufacturing)

[0111] A 50 mL container, nitrogen-replaced, was placed at 30°C. 20 g of the prepared reaction stock solution B, after being nitrogen-replaced and at 30°C, was injected into the container using a glass syringe, followed by stirring. Next, 0.2 g of the prepared activator solution A was injected into the container using the glass syringe, and mixing was performed for 10 seconds. During this time, as the polymerization reaction proceeded, the solution transitioned to a gel state, producing white smoke. In this embodiment, the time from the start of mixing of activator solution A and reaction stock solution B until the transition to a gel state is called the "gelation time," and the time until the production of white smoke is called the "curing time." In Example 1, the gelation time was 15 seconds, and the curing time was 70 seconds, resulting in a polymer of dicyclopentadiene and tricyclopentadiene. Furthermore, during polymerization, to evaluate mold release properties, polymerization was performed by forming a thin sheet-like polymer portion for mold release property evaluation.

[0112] The resulting polymer was then evaluated for its release properties and filler properties using the following method. The results are shown in Table 1.

[0113] (Mold release properties)

[0114] For the thin-plate polymer portion used for evaluating the release properties of the obtained polymer, the hardness is determined by measuring the release time, and the evaluation is carried out according to the following criteria.

[0115] ○: The demolding time for A4-sized boards is within 5 seconds.

[0116] ×: Demolding time for A4-sized boards exceeds 5 seconds.

[0117] (Filling)

[0118] For the obtained polymer, the filling property is evaluated by confirming the presence of unfilled portions, according to the following criteria.

[0119] ○: Filled with no missing parts in the A4 board.

[0120] ×: There are missing parts on the A4 sheet that have not been filled.

[0121] (Example 2)

[0122] Using a portion of the viscous substance obtained in Example 1, a hexane suspension was prepared by adding hexane. The hexane suspension was then centrifuged to precipitate the insoluble matter. The yellowish-brown solution of the supernatant was collected and left to stand at room temperature overnight. The compound represented by formula (15) was then separated as yellow needle-like crystals. Furthermore, the obtained needle-like crystals were subjected to… 183 WOCl4 was not detected by W-NMR analysis. Then, under a nitrogen atmosphere, 5 parts of the isolated compound represented by formula (15) and 0.15 parts of WOCl4 (3 parts of WOCl4 relative to 100 parts of the compound represented by formula (15)) were added to a glass vial. While stirring, 45 parts of a mixture of 90% dicyclopentadiene and 10% tricyclopentadiene norbornene monomers (RIM-M) were added using a glass syringe to obtain a catalyst solution. The viscosity of the catalyst solution was measured using a type B viscometer after stirring for 10 minutes, and the result was 34.6 mPa·s.

[0123] Then, except for using the catalyst solution obtained above, reaction stock solution B was prepared in the same manner as in Example 1, and activator solution A obtained in the same manner as in Example 1 was used to obtain the polymer, which was then evaluated in the same way. The results are shown in Table 1.

[0124] (Example 3)

[0125] The procedure was carried out in the same manner as in Example 2, using a portion of the viscous substance obtained in Example 1, as yellow needle-like crystals, to separate the compound represented by formula (15). Furthermore, the obtained needle-like crystals were subjected to… 183WOCl4 was not detected by W-NMR analysis. Then, under a nitrogen atmosphere, 4.95 parts of the isolated compound represented by formula (15) and 0.5 parts of WOCl4 (10.1 parts of WOCl4 relative to 100 parts of the compound represented by formula (15)) were added to a glass vial. While stirring, 44.55 parts of a mixture of 90% dicyclopentadiene and 10% tricyclopentadiene norbornene monomers (RIM-M) were added using a glass syringe to obtain a catalyst solution. After stirring the catalyst solution for 10 minutes, the viscosity was measured using a type B viscometer, and the result was 3840 mPa·s.

[0126] Then, except for using the catalyst solution obtained above, reaction stock solution B was prepared in the same manner as in Example 1, and activator solution A obtained in the same manner as in Example 1 was used to obtain the polymer, which was then evaluated in the same way. The results are shown in Table 1.

[0127] (Comparative Example 1)

[0128] The procedure was carried out in the same manner as in Example 2, using a portion of the viscous substance obtained in Example 1, as yellow needle-like crystals, to separate the compound represented by formula (15). Furthermore, the obtained needle-like crystals were subjected to… 183 WOCl4 was not detected by W-NMR analysis. Then, under a nitrogen atmosphere, two parts of the isolated compound represented by formula (15) were added to a glass vial. While stirring, 100 parts of a mixture of norbornene monomers (RIM-M) consisting of 90% dicyclopentadiene and 10% tricyclopentadiene were added using a glass syringe to obtain a catalyst solution. That is, in Comparative Example 1, WOCl4 was not present in the catalyst solution.

[0129] Then, except for using the catalyst solution obtained above, reaction stock solution B was prepared in the same manner as in Example 1, and activator solution A obtained in the same manner as in Example 1 was used to obtain the polymer, which was then evaluated in the same way. The results are shown in Table 1.

[0130] [Table 1]

[0131]

[0132] The results in Table 1 also clearly confirm that, based on a catalyst liquid containing 0.5 to 20 parts by weight of MoOCl4 and / or WOCl4 relative to 100 parts by weight of the metal oxide complex represented by general formula (1), the polymerizable composition obtained by coordinating the catalyst liquid can have excellent release properties and filler properties.

Claims

1. A catalyst liquid containing a metal oxo complex represented by the following general formula (1), and further containing MoOCl4 and / or WOCl4, wherein the total content of MoOCl4 and WOCl4 is 0.5 to 20 parts by weight relative to 100 parts by weight of the metal oxo complex. In the above general formula (1), M represents a molybdenum atom or a tungsten atom, A represents a carbon atom, a silicon atom, a germanium atom, a tin atom, or a lead atom, and R... 1 ~R 5 Each can independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms that can have substituents (either straight or branched), or an aryl group with 6 to 20 carbon atoms that can have substituents, R 1 ~R 3 They can bond with each other to form a ring.

2. The catalyst liquid according to claim 1 further contains norbornene monomers.

3. The catalyst liquid according to claim 1 or 2, wherein, In the general formula (1), A is a carbon atom or a silicon atom.

4. The catalyst solution according to any one of claims 1 to 3, wherein, In the general formula (1), R 4 and R 5 At least one of them is methyl or tert-butyl.

5. The catalyst solution according to any one of claims 1 to 4, wherein, In the general formula (1), R 1 R 2 It consists of alkyl groups with 1 to 20 carbon atoms that are straight or branched and can have substituents, and which are bonded together to form a ring.

6. A method for manufacturing a catalyst liquid, comprising the method for manufacturing the catalyst liquid according to any one of claims 1 to 5, comprising: The first step involves reacting MoCl6 and / or WCl6 with a ketone compound in an aliphatic solvent to obtain a solution containing MoOCl4 and / or WOCl4. In the second step, the compound represented by the following general formula (2) is reacted with the solution containing MoOCl4 and / or WOCl4 obtained in the first step to obtain a solution containing the compound represented by the following general formula (3); as well as In the third step, the compound represented by the following general formula (4) is reacted with the solution containing the compound represented by the general formula (3) obtained in the second step, thereby obtaining a catalyst solution containing the metal oxo complex represented by the general formula (1) and also containing MoOCl4 and / or WOCl4. In the above general formulas (2) to (4), A represents a carbon atom, silicon atom, germanium atom, tin atom, or lead atom, and R... 1 ~R 5 Each can independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms that can have substituents (either straight or branched), or an aryl group with 6 to 20 carbon atoms that can have substituents, R 1 ~R 3 They can bond with each other to form a ring.

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