Iron complex catalyst encapsulated in a resin, addition-curable composition containing the same, and method for producing the iron complex catalyst encapsulated in a resin

Abstract

Provided are an iron complex catalyst encapsulated in a resin, which eliminates the need to handle and store the iron complex catalyst, which is unstable in air, in an inert atmosphere, an addition-curable composition containing the same, and a method for producing the same. An iron complex catalyst encapsulated in a resin, The iron complex catalyst is a catalyst for the hydrosilylation reaction of alkenes and a catalyst for the dehydrocoupling reaction of silanes. The addition-curable composition contains the iron complex catalyst encapsulated in the resin. The method for producing the resin-encapsulated iron complex catalyst includes a step of removing the solvent from a mixture of the iron complex catalyst, the resin, and the solvent to obtain the resin-encapsulated iron complex catalyst.

Description

[Technical Field]

[0001] The present invention relates to an iron complex catalyst that is encapsulated in a resin, an addition-curable composition containing the same, and a method for producing the iron complex catalyst encapsulated in a resin. [Background technology]

[0002] One method for synthesizing organosilicon compounds is the hydrosilylation of carbon-carbon multiple bonds. Transition metal catalysts are primarily used for hydrosilylation reactions, but industrially, noble metal catalysts containing noble metals such as platinum or rhodium are known (WO 2011 / 6049).

[0003] Various metal complex catalysts using metals that are cheaper than precious metal catalysts have been developed. For example, an iron complex catalyst with the following structure has been reported for hydrosilylation reactions (JP 2020-50637 A).

[0004] [ka]

[0005] A platinum catalyst for hydrosilylation reactions microencapsulated in a thermoplastic resin with a softening point of 40°C to 260°C has also been reported (Japanese Patent Laid-Open No. 2-14244). This microencapsulated catalyst is contained in a one-package organopolysiloxane composition containing an organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule. In such compositions, the catalyst does not react with the substrate organopolysiloxane even at room temperature, and the composition is reported to have excellent storage stability.

[0006] Another known method for synthesizing organosilicon compounds is the dehydrogenative coupling reaction of silane, which also primarily uses a transition metal catalyst (see JP-A-6-145360 and JP-A-2010-47699). Summary of the Invention

[0007] The present invention provides an iron complex catalyst encapsulated in a resin, comprising: The iron complex catalyst is a resin-encapsulated iron complex catalyst that is a catalyst for the hydrosilylation reaction of alkenes, a catalyst for the dehydrocoupling reaction of silanes, or a catalyst for the addition curing reaction of silicones.

[0008] When developing various iron complex catalysts for the synthesis of the organosilicon compounds, the present inventors developed an iron complex catalyst that met requirements such as high reaction conversion rate, fast reaction rate, and a wide range of applicable substrates (see JP 2020-117474 A). However, such iron complex catalysts were unstable in air and therefore needed to be stored under an inert atmosphere.

[0009] The present invention provides an iron complex catalyst encapsulated in a resin, which eliminates the need to handle or store the iron complex catalyst, which is unstable in air, under an inert atmosphere, and an addition-curable composition containing the same.

[0010] The present invention provides an iron complex catalyst encapsulated in a resin, comprising: The iron complex catalyst is a catalyst for hydrosilylation of an alkene, a catalyst for the dehydrocoupling reaction of silanes, or A catalyst for silicone addition curing reactions, It is an iron complex catalyst encapsulated in a resin.

[0011] The present invention also provides an addition-curable composition comprising an iron complex catalyst encapsulated in the resin of the present invention.

[0012] The present invention also relates to a method for producing the resin-encapsulated iron complex catalyst of the present invention, which comprises removing the solvent from a mixture of the iron complex catalyst, the resin, and the solvent to obtain the resin-encapsulated iron complex catalyst.

[0013] The iron complex catalyst encapsulated in the resin of the present invention is easy to handle and store because it is not necessary to handle or store the iron complex catalyst, which is unstable in air, under an inert atmosphere.Furthermore, an addition-curable composition containing such a resin-encapsulated iron complex catalyst is also easy to handle and store because it is not necessary to handle or store it under an inert atmosphere.

[0014] For example, in the case of hydrosilylation-curable compositions, the curable components in the composition are crosslinked by a reactive catalyst, such as a platinum-group catalyst. That is, curing begins when the curable components come into contact with the reactive catalyst. Therefore, to prevent undesired curing, it is necessary to prevent contact between the reactive catalyst and the curable components during storage of such compositions.

[0015] One way to prevent contact between the reactive catalyst and the curable component is to physically separate the components, i.e., to use a two-component composition containing a composition containing a reactive catalyst and a composition containing a curable component, which is prepared by mixing the composition containing the reactive catalyst and the composition containing the curable component, thereby bringing the curable component into contact with the reactive catalyst and causing curing.

[0016] Another approach is to use a one-component composition in which the reactive catalyst and the curable component are present in the same system. In this one-component composition, the reactive catalyst is coated or microencapsulated to ensure that it does not come into contact with the curable component. A thermoplastic resin is used as the coating or microencapsulation material. For example, a one-component composition containing a reactive catalyst coated or microencapsulated with a specific thermoplastic resin can be heated to a specific temperature to release the reactive catalyst from the coating or microencapsulation, allowing it to come into contact with the curable component and produce the desired cure.

[0017] The present invention aims to eliminate the need to handle or store the air-unstable iron complex catalyst under an inert atmosphere. On the other hand, in the case of the one-component and two-component compositions, the aim is to ensure that the reactive catalyst and the curable component do not come into contact with each other. Therefore, the aim of the present invention is clearly different from the aim of the one-component and two-component compositions known in the prior art.

[0018] <Iron complex catalyst encapsulated in resin> The present invention is an iron complex catalyst encapsulated in a resin. <<Resin>> The resin preferably includes a silicone resin that is solid at room temperature. The room temperature means 25°C ± 1°C. The silicone resin is, for example, one or more selected from the group consisting of methylsilicone resin, phenylsilicone resin, and methylphenylsilicone resin, and a methylsilicone resin or a phenylsilicone resin alone or in combination is preferred. These silicone resins may have reactive functional groups (silanol groups, alkoxy groups, vinyl groups, hexenyl groups, octenyl groups, epoxy groups, methacrylic groups, etc.).

[0019] The silicone resin has at least one of four components represented by the following chemical formula: T component (T unit: trifunctional organosilsesquioxane unit), D component (D unit: difunctional diorganosiloxane unit), M component (M unit: monofunctional triorganosiloxy unit), and Q component (Q unit: tetrafunctional unit), and preferably contains the T component or both the D component and the T component. Examples of such silicone resins include T resins consisting solely of the T component, MTQ resins containing a combination of the M component, the T component, and the Q component, MDTQ resins containing a combination of the M component, the D component, the T component, and the Q component, DT resins containing a combination of the D component and the T component, and TDQ resins containing a combination of the D component, the T component, and the Q component. Preferred examples of such silicone resins include T resins and DT resins.

[0020] [ka]

[0021] In the formula, R is, independently of each other, an alkyl group (e.g., a methyl group) and / or an aryl group (e.g., a phenyl group).

[0022] In the silicone resin, the ratio of the T component to all the components contained in the silicone resin (T component, D component, M component, and Q component) is, for example, 70% or more, preferably 70 to 100%, more preferably 85 to 100%, and even more preferably 90 to 100%.

[0023] Specifically, the T component of the silicone resin includes at least one of the following structures: T0 component, T1 component, T2 component, and T3 component.

[0024] [ka]

[0025] In the formula, R a are, independently of each other, alkyl groups (e.g., methyl groups) and / or aryl groups (e.g., phenyl groups). b are, independently of each other, alkyl groups (e.g., methyl groups, ethyl groups, etc.) and / or hydrogen (H).

[0026] With respect to the total T components, for example, the content of T1 components is 0 to 5%, the content of T2 components is 10 to 70%, and the content of T3 components is 20 to 90%.

[0027] The silicone resin may also contain the D component. The total amount of the D component is 0 to 10%, preferably 0 to 5%, relative to the T component. Specifically, the D component contains at least one of the structures shown below: D0 component, D1 component, and D2 component. For example, the content of the D1 component is 10 to 40%, and the content of the D2 component is 60 to 90% relative to the total amount of the D component.

[0028] [ka]

[0029] In the formula, R a R is an alkyl group (e.g., a methyl group) and / or an aryl group (e.g., a phenyl group). b is an alkyl group (e.g., a methyl group, an ethyl group, etc.) and / or hydrogen (H).

[0030] The percentage of T and D components is 29 It can be determined by the area ratio of Si-NMR.

[0031] <<Iron complex catalyst>> The iron complex catalyst is a catalyst for the hydrosilylation reaction of an alkene, a catalyst for the dehydrogenative coupling reaction of a silane, or a catalyst for the addition curing reaction of a silicone. These iron complex catalysts are usually unstable in air and must be handled under an inert atmosphere. The iron complex catalyst encapsulated in the resin of the present invention is stable in air and does not need to be handled or stored under an inert atmosphere, making it easy to handle and store.

[0032] The iron complex catalyst is, for example, a catalyst represented by the following formula (I).

[0033] (L 1 )FeX n1 (I)

[0034] In the formula (I), n1 is 2 or 3. Each X is independently -SC(=O)CH3 or -OC(=O)R 10 Represents R 10 represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. Two or more of X are -OC(=O)R 10 If R 10 They may be linked together to form a ring structure. Also, if n1 is 3, the two Xs together

[0035] [ka]

[0036] (R 10 represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. * represents the bonding position.) where one X is -SC(=O)CH3 or -OC(=O)R 10 (R 10 represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. L 1 represents a tridentate ligand represented by the following general formula (L-1).

[0037] [ka]

[0038] [In formula (L-1), R 1 and R 2 each independently represents a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, or a halogen atom. The Two R's 3 each independently represents an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent. n2 is an integer of 0 to 4. n3 is an integer of 0 to 5. However, R 1 is attached to a carbon atom of the pyridine skeleton. When n2 is an integer between 2 and 4, R 1 The hydrocarbon groups may be linked together to form a cyclic structure. R 2 is attached to a carbon atom of the quinoline skeleton. When n3 is an integer between 2 and 5, R 2 The hydrocarbon groups may be linked to each other to form a cyclic structure.]

[0039] In the formula (I), n1 is 2 or 3. In the formula (I), each X is independently -SC(=O)CH3 or -OC(=O)R 10 Represents R 10 represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent; and two or more of X are -OC(=O)R. 10 If R 10 They may be linked together to form a ring structure.

[0040] R 10 The hydrocarbon group in R may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group. 10 The hydrocarbon group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 8 carbon atoms.

[0041] R 10 Examples of the substituent that the hydrocarbon group may have include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a silyl group, an amino group, and a methoxy group.

[0042] R 10 Examples of the alkyl group include a methyl group (-CH3), a t-butyl group (-C(CH3)3), a trifluoromethyl group (-CF3), and an ethylpentyl group (-CH(C2H5)C4H9).

[0043] R 10 The cyclic structure formed by linking together may be an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, or a heterocyclic ring.

[0044] In the above formula (I), L 1 represents a tridentate ligand represented by general formula (L-1). In the formula (L-1), R 1 and R 2 each independently represents a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, or a halogen atom.

[0045] R 1 and R2 Examples of the halogen atom in the formula include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0046] R 1 Examples of the alkyl group include a methyl group (-CH3), an ethyl group (-CH2CH3), an n-propyl group (-CH2CH2CH3), an i-propyl group (-CH(CH3)2), an n-butyl group (-CH2CH2CH2CH3), a t-butyl group (-C(CH3)3), a pentyl group (-CH2(CH2)3CH3), a hexyl group (-CH2(CH2)4CH3), a phenyl group, a 2,6-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,4,6-trimethylphenyl group, a 2,6-diisopropylphenyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0047] R 2 For example, R 1 Examples of the groups include the same as those exemplified in the above.

[0048] R 1 and R 2 The substituents which the hydrocarbon group may have in the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0049] R 1 and R 2 Examples of the substituent that the aromatic hydrocarbon group in the formula (I) may have include a hydrocarbon group having 1 to 6 carbon atoms, an aromatic hydrocarbon group, an alkoxy group, a silyl group, and a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), and specific examples thereof include an alkyl group having 1 to 6 carbon atoms.

[0050] In the formula (L-1), two R 3 each independently represents an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent.

[0051] R 3 The "alkyl group" in the above is not limited to a straight-chain alkyl group, but also includes alkyl groups having a branched structure or a cyclic structure.

[0052] R 3 Examples of the alkyl group include a methyl group (-CH3), an ethyl group (-CH2CH3), an n-propyl group (-CH2CH2CH3), an i-propyl group (-CH(CH3)2), an n-butyl group (-CH2CH2CH2CH3), a t-butyl group (-C(CH3)3), a pentyl group (-CH2(CH2)3CH3), a hexyl group (-CH2(CH2)4CH3), a heptyl group (-CH2(CH2)5CH3), an octyl group (-CH2(CH2)6CH3), a nonyl group (-CH2(CH2)7CH3), a decyl group (-CH2(CH2)8CH3), a phenyl group, a 2,6-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,4,6-trimethylphenyl group, and a 2,6-diisopropylphenyl group.

[0053] R 3 Examples of the substituent that the alkyl group in the formula (I) may have include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0054] R 3 Examples of the substituent that the aromatic hydrocarbon group in the formula (I) may have include a hydrocarbon group having 1 to 6 carbon atoms, an aromatic hydrocarbon group, an alkoxy group, a silyl group, and a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), and specific examples thereof include an alkyl group having 1 to 6 carbon atoms.

[0055] In the formula (L-1), n2 represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0056] n3 is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

[0057] R in the formula (L-1) 1 is attached to a carbon atom of the pyridine skeleton. 1 is bonded to the carbon atom of the pyridine skeleton, R is bonded to the carbon atom that constitutes the pyridine ring. 1 This means that the two are bonded together.

[0058] In the formula (L-1), when n2 is an integer of 2 to 4, R 1 The hydrocarbon groups may be linked together to form a cyclic structure. For example, when n2 is 2, two R 1 are linked to form a cycloheptane structure, a cycloheptene structure, a cyclohexane structure, a cyclohexene structure, etc.

[0059] R in the formula (L-1) 2 is attached to a carbon atom of the quinoline skeleton. 2 is bonded to the carbon atom of the quinoline skeleton, R is bonded to the carbon atom that constitutes the quinoline ring. 2 This means that the two are bonded together.

[0060] In the formula (L-1), when n3 is an integer of 2 to 5, R 2 The hydrocarbon groups may be linked together to form a cyclic structure. For example, when n3 is 2, two R 2 are linked to form a cycloheptane structure, a cycloheptene structure, a cyclohexane structure, a cyclohexene structure, etc.

[0061] Examples of the metal complex compound represented by the general formula (I) include the following compounds.

[0062] In this specification, "iPr" in the chemical formulas represents an isopropyl group, "Ph" represents a phenyl group, "Pv" represents a pivaloyl group, and "Ac" represents an acetyl group.

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] The iron complex catalyst is preferably a compound represented by formula (1).

[0067] [ka]

[0068] The iron complex catalyst can be produced, for example, according to the method described in the following document. Patent Publication No. 2020-117474; Kamitani et al., Bull. Chem. Soc. Jpn., 2018, 91, 1429-1435;Kamitani et al., Chem. Lett., 2019, 48, 1196-1198; Kamitani, et al, Organometallics, 2020, 39, 3535-3539; Kamitani, Chem. Comm., 2021, 57, 13246-13258; Kamitani, et. al, Organometallics, 2023, 42, 1839-1848.

[0069] The iron complex catalyst encapsulated in the resin contains, for example, 0.001 to 50 mass %, preferably 0.01 to 30 mass %, and more preferably 0.1 to 20 mass % of the iron complex catalyst.

[0070] <Method for producing resin-encapsulated iron complex catalyst> The iron complex catalyst encapsulated in the resin can be obtained, for example, by removing the solvent from a mixture of the iron complex catalyst, the resin, and the solvent.

[0071] <<A mixture of iron complex catalyst, resin and solvent>> The mixture of the iron complex catalyst, resin, and solvent can be obtained by adding the iron complex catalyst and the resin to a solvent and dissolving or mixing them. As described above, the iron complex catalyst is a catalyst for the hydrosilylation reaction of an alkene, a catalyst for the dehydrocoupling reaction of a silane, or a catalyst for the silicone addition curing reaction, and may be produced according to known literature or may be commercially available.

[0072] The resin may be prepared according to known literature or may be commercially available.

[0073] Examples of the solvent include hydrocarbon solvents such as hexane, benzene, and toluene, and ether solvents such as diethyl ether, 1,4-dioxane, and tetrahydrofuran (THF).One type of solvent may be used alone, or two or more types may be used in combination.

[0074] The amount of the resin used relative to 1 part by mass of the iron complex catalyst is, for example, 1.0 to 10,000 parts by mass, preferably 1.0 to 1,000 parts by mass, and more preferably 1.1 to 500 parts by mass.

[0075] In the step of adding the iron complex catalyst and the resin to a solvent and dissolving or mixing them, the reaction conditions such as the reaction temperature and reaction time are not particularly limited. The reaction temperature is usually 20°C or higher, preferably 25°C (room temperature) or higher, and usually 150°C or lower, preferably 100°C or lower, more preferably 80°C or lower.

[0076] <<Step of Removing the Solvent from the Mixture of Iron Complex Catalyst, Resin, and Solvent>> Methods for removing the solvent from a mixture of an iron complex catalyst, a resin, and a solvent include stirring, spraying, and airflow, but the method is not limited thereto. For example, the solvent can be removed by heat drying and / or vacuum drying. The drying temperature is usually 20°C or higher, preferably 25°C (room temperature) or higher, and usually 150°C or lower, preferably 100°C or lower, and more preferably 80°C or lower. Vacuum drying is performed as needed, but the vacuum conditions are not particularly specified. A powder can be obtained by removing the solvent. The shape, particle size, and particle diameter of this powder are not particularly limited.

[0077] <Method for Hydrosilylation of Alkenes> The present invention relates to a method for hydrosilylation of an alkene by reacting an alkene with a hydrosilane in the presence of an iron complex catalyst encapsulated in the resin of the present invention, whereby an organosilicon compound is obtained by hydrosilylation of the alkene.

[0078] In the method for hydrosilylation of an alkene of the present invention, the alkene, the hydrosilane, and the iron complex catalyst encapsulated in the resin of the present invention are heated, whereby the iron complex catalyst excluding the resin is diffused into the system, thereby inducing a reaction between the alkene and the hydrosilane. Alternatively, a solvent can be applied to the alkene, the hydrosilane, and the iron complex catalyst encapsulated in the resin of the present invention to produce the iron complex catalyst excluding the resin, thereby inducing a reaction between the alkene and the hydrosilane.

[0079] <<Alkene>> The alkene may be, for example, a compound represented by the following formula (II).

[0080] [ka]

[0081] In the formula (II), R 21 , R 22 , R 23 and R 24each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent containing at least one selected from the group consisting of a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a halogen atom. 21 , R 22 , R 23 and R 24 at least one of R is a hydrocarbon group; 21 , R 22 , R 23 and R 24 When two or more of the groups are hydrocarbon groups, the two or more hydrocarbon groups may be linked to form a cyclic structure.

[0082] Specific examples of alkenes include 1-butene, 1-hexene, 3,3-dimethyl-1-butene, 1-octene, 1-decene, 1-dodecene, cis-4-octene, trans-5-decene, 4-phenyl-1-butene, 6,6-dimethyl-1-heptene, 4,4-dimethyl-1-hexene, styrene, α-methylstyrene, p-fluorostyrene, p-bromostyrene, p-methoxystyrene, cyclohexene, 6-chloro-1-hexene, 3-(dimethylamino)-1-propene, and allyl phenyl sulfide.

[0083] <<Hydrosilanes>> The hydrosilane includes a compound represented by the following formula (III).

[0084] [ka]

[0085] In the formula (III), R 5 , R 6 and R 7 each independently represents a hydrogen atom, a halogen atom, a siloxy group, a polysiloxy group having 1 to 50 silicon atoms, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent containing at least one selected from the group consisting of a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a halogen atom.

[0086] Examples of hydrosilanes include diethylsilane, phenylsilane, triphenylsilane, diphenylsilane, phenyl(methyl)silane, phenyldi(methyl)silane, trimethoxysilane, triethoxysilane, methyldimethoxysilane, methyldiethoxysilane, triethoxysilane, triethylsilane, and diethoxymethylsilane.

[0087] <<Amount of alkene and hydrosilane used>> The amounts of alkene and hydrosilane used in the reaction can be appropriately selected depending on the purpose, but the amount of alkene used is usually 0.2 equivalents or more, preferably 0.5 equivalents or more, and more preferably 1 equivalent or more, relative to 1.0 equivalent of hydrosilane, and is usually 50 equivalents or less, preferably 20 equivalents or less, and more preferably 15 equivalents or less. Within the above ranges, the organosilicon compound can be produced in a higher yield.

[0088] <<Amount of iron complex catalyst encapsulated in resin>> The amount of the iron complex catalyst encapsulated in the resin used can be appropriately selected depending on the purpose. For example, the amount used (the amount of the iron complex itself excluding the resin) is usually 0.00001 equivalents or more, preferably 0.0001 equivalents or more, and more preferably 0.001 equivalents or more, relative to 1 equivalent of hydrosilane, and is usually 1 equivalent or less, preferably 0.1 equivalents or less, and more preferably 0.01 equivalents or less. Within the above range, a sufficient reaction rate can be obtained, purification is facilitated, and the organosilicon compound can be produced in a higher yield. The above-mentioned iron complex catalyst encapsulated in the resin may be used alone or in combination of two or more. When two or more types are combined, the total amount used is preferably within the above range.

[0089] <<Solvent>> The reaction step may or may not involve the use of a solvent, but can be suitably carried out without a solvent. When no solvent is used, for example, hydrosilane may also be used as a solvent. When a solvent is used, the type of solvent is not particularly limited and can be appropriately selected depending on the purpose. Specific examples include hydrocarbon solvents such as hexane, benzene, and toluene, and ether solvents such as diethyl ether, 1,4-dioxane, and tetrahydrofuran (THF). One type of solvent may be used alone, or two or more types may be used in combination.

[0090] <<Reaction temperature, reaction time>> There are no particular limitations on reaction conditions such as reaction temperature and reaction time. The reaction temperature is usually 20°C or higher, preferably 25°C (room temperature) or higher, and usually 150°C or lower, preferably 100°C or lower, and more preferably 80°C or lower. Within the above range, organosilicon compounds can be produced in a higher yield.

[0091] The reaction time of the reaction step is not particularly limited, but is usually 1 hour or more, preferably 3 hours or more.

[0092] <<Reaction atmosphere>> The reaction can usually be carried out in an air atmosphere or an inert atmosphere such as nitrogen or argon.

[0093] <Method for Dehydrogenative Coupling of Silane Compounds> The present invention relates to a method for dehydrogenative coupling of a silane compound by reacting the silane compound with the iron complex catalyst encapsulated in the resin of the present invention, which produces a polysilane.

[0094] In the method of the present invention for carrying out the dehydrogenative coupling reaction of a silane compound, the silane compound and the iron complex catalyst encapsulated in the resin of the present invention are heated to generate the iron complex catalyst, which then initiates the dehydrogenative coupling reaction of the silane compound. Alternatively, a solvent can be applied to the silane compound and the iron complex catalyst encapsulated in the resin of the present invention to generate the iron complex catalyst, which then initiates the dehydrogenative coupling reaction of the silane compound.

[0095] <<Silane compounds>> The silane compound includes a compound represented by the following formula (IV).

[0096] [ka]

[0097] In the formula (IV), R 25 , R 26 and R 27 each independently represents a hydrogen atom, a halogen atom, a siloxy group, a polysiloxy group having 1 to 50 silicon atoms, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent containing at least one selected from the group consisting of a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a halogen atom.

[0098] Examples of the silane compound include triethylsilane, phenylsilane, triphenylsilane, diphenyl(methyl)silane, phenyldi(methyl)silane, trimethoxysilane, triethoxysilane, methyldimethoxysilane, methyldiethoxysilane, triethylsilane, and diethoxymethylsilane.

[0099] <<Amount of iron complex catalyst encapsulated in resin>> The amount of the iron complex catalyst encapsulated in the resin can be appropriately selected depending on the purpose. For example, the amount (the amount of the iron complex itself excluding the resin) is usually 0.00001 equivalents or more, preferably 0.0001 equivalents or more, and more preferably 0.001 equivalents or more, relative to 1 equivalent of the silane compound, and is usually 1 equivalent or less, preferably 0.1 equivalents or less, and more preferably 0.01 equivalents or less. Within the above range, a sufficient reaction rate can be obtained, purification is easy, and the silane polymer can be produced with a high yield. The above-mentioned resin-encapsulated iron complex catalysts may be used alone or in combination of two or more. When two or more types are combined, the total amount used is preferably within the above range.

[0100] <<Solvent>> The reaction step may or may not use a solvent, but can be suitably carried out without a solvent. In the case of no solvent, for example, a silane compound may also be used as a solvent. When a solvent is used, the type of solvent is not particularly limited and can be appropriately selected depending on the purpose. Specific examples include hydrocarbon solvents such as hexane, benzene, and toluene, and ether solvents such as diethyl ether, 1,4-dioxane, and tetrahydrofuran (THF). One type of solvent may be used alone, or two or more types may be used in combination.

[0101] <<Reaction temperature, reaction time>> The reaction conditions, such as the reaction temperature and reaction time, are not particularly limited. The reaction temperature is usually 20° C. or higher, preferably 25° C. (room temperature) or higher, and usually 150° C. or lower, preferably 100° C. or lower, and more preferably 80° C. or lower. If the reaction temperature is within the above range, polysilane can be produced in a high yield.

[0102] The reaction time in the reaction step is usually 1 hour or longer, preferably 3 hours or longer, and usually 60 hours or shorter, preferably 50 hours or shorter, more preferably 48 hours or shorter.

[0103] <<Atmosphere>> The reaction can usually be carried out in an air atmosphere or an inert atmosphere such as nitrogen or argon.

[0104] <Addition-curable composition and addition-curable reaction> The present invention relates to an addition-curable composition containing an iron complex catalyst encapsulated in a resin of the present invention. Such an addition-curable composition containing an iron complex catalyst encapsulated in a resin is easy to handle and store because it does not need to be handled or stored under an inert atmosphere. The addition-curable composition preferably further contains an alkenyl group-containing organopolysiloxane and a SiH group-containing organopolysiloxane.

[0105] By heating the addition-curable composition of the present invention, which contains an alkenyl-group-containing organopolysiloxane, a SiH-group-containing organopolysiloxane, and the iron complex catalyst encapsulated in the resin of the present invention, the iron complex catalyst is generated, which then reacts with the alkenyl-group-containing organopolysiloxane and the SiH-group-containing organopolysiloxane (crosslinking component), yielding a cured product (addition-curable reaction product). Alternatively, a solvent can be applied to the alkenyl-group-containing organopolysiloxane, the SiH-group-containing organopolysiloxane (crosslinking component), and the iron complex catalyst encapsulated in the resin of the present invention, which then generates the iron complex catalyst, which then reacts with the alkenyl-group-containing organopolysiloxane and the SiH-group-containing organopolysiloxane (crosslinking component), yielding a cured product (addition-curable reaction product).

[0106] <<Alkenyl group-containing organopolysiloxane>> The alkenyl group-containing organopolysiloxane may, for example, be an organopolysiloxane having an average unit formula: R'aSiO (4-a) / 2 wherein R' is a substituted or unsubstituted monovalent hydrocarbon group; a is a number between 1.0 and 2.3, At least two silicon-bonded alkenyl groups in the molecule It is expressed as:

[0107] The aforesaid R’ is a substituted or unsubstituted monovalent hydrocarbon group, for example, a monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, an aryl group, an aralkyl group, etc. Examples of the substituent of the substituted monovalent hydrocarbon group include a halogen atom, an alkoxy group, etc. The aforesaid a is a number from 1.0 to 2.3.

[0108] <<Usage amount of iron complex catalyst encapsulated in resin>> Examples of the SiH group-containing organopolysiloxane include organohydrogenpolysiloxane. The SiH group-containing organopolysiloxane acts as a crosslinking component, and a cured product is formed by the addition reaction (hydrosilylation) between the SiH group in this component and the alkenyl group of the alkenyl group-containing organopolysiloxane. Any SiH group-containing organopolysiloxane having two or more hydrogen atoms (i.e., SiH groups) bonded to silicon atoms in one molecule can be used as a crosslinking component. The molecular structure of this SiH group-containing organopolysiloxane may be linear, cyclic, branched, or three-dimensional network structure. In addition, the number of silicon atoms (i.e., the degree of polymerization) in one molecule of the SiH group-containing organopolysiloxane is preferably 2 to 1000, particularly about 2 to 300, and such a one can be preferably used as a crosslinking component.

[0109] The blending ratio (SiH group-containing organopolysiloxane / alkenyl group-containing organopolysiloxane, mass ratio) of the aforesaid SiH group-containing organopolysiloxane and the alkenyl group-containing organopolysiloxane is, for example, an amount in the range of 0.05 to 10, preferably in the range of 0.01 to 5. Also, the blending ratio (Si-H group of SiH group-containing organopolysiloxane / alkenyl group of alkenyl group-containing organopolysiloxane, equivalent ratio) of the aforesaid SiH group-containing organopolysiloxane and the alkenyl group-containing organopolysiloxane is, for example, in the range of 0.01 to 10, preferably in the range of 0.1 to 5.

[0110] <<Usage amount of iron complex catalyst encapsulated in resin>> The amount of the iron complex catalyst encapsulated in the resin can be appropriately selected depending on the purpose. For example, the amount used is usually 0.00001 equivalents or more, preferably 0.0001 equivalents or more, more preferably 0.001 equivalents or more, relative to 1 equivalent of the alkenyl group-containing organopolysiloxane, and is usually 1 equivalent or less, preferably 0.1 equivalents or less, more preferably 0.01 equivalents or less. Within the above range, a sufficient reaction rate can be obtained, purification is easy, and a cured product can be produced with a high yield. The above-mentioned resin-encapsulated iron complex catalysts may be used alone or in combination of two or more. When two or more types are combined, it is preferable that the total amount used be within the above range.

[0111] <<Solvent>> The reaction step may or may not use a solvent, but can be suitably carried out without a solvent. In the case of no solvent, for example, the crosslinking component may also be used as the solvent. When a solvent is used, the type of solvent is not particularly limited and can be appropriately selected depending on the purpose. Specific examples include hydrocarbon solvents such as hexane, benzene, and toluene, and ether solvents such as diethyl ether, 1,4-dioxane, and tetrahydrofuran (THF). One type of solvent may be used alone, or two or more types may be used in combination.

[0112] <<Reaction temperature, reaction time>> The reaction conditions, such as reaction temperature and reaction time, are not particularly limited. The reaction temperature is usually 20° C. or higher, preferably 25° C. (room temperature) or higher, and usually 150° C. or lower, preferably 100° C. or lower, and more preferably 80° C. or lower. Within the above range, the silane polymer can be produced in a high yield.

[0113] The reaction time in the reaction step is usually 1 hour or longer, preferably 3 hours or longer, and usually 60 hours or shorter, preferably 50 hours or shorter, more preferably 48 hours or shorter.

[0114] <<Atmosphere>> The reaction can usually be carried out in an air atmosphere or an inert atmosphere such as nitrogen or argon.

[0115] The present invention includes the following aspects.

[0116] [Item 1] An iron complex catalyst encapsulated in a resin, The iron complex catalyst is a resin-encapsulated iron complex catalyst that is a catalyst for the hydrosilylation reaction of an alkene, a catalyst for the dehydrocoupling reaction of a silane, or a catalyst for the addition curing reaction of a silicone.

[0117] [Item 2] The iron complex catalyst encapsulated in a resin according to Item 1, wherein the resin contains a silicone resin that is solid at room temperature.

[0118] [Item 3] The resin-encapsulated iron complex catalyst according to Item 2, wherein the silicone resin is at least one selected from the group consisting of a methylsilicone resin, a phenylsilicone resin, and a methylphenylsilicone resin, and preferably a methylsilicone resin, a phenylsilicone resin, or a combination of both.

[0119] [Item 4] The iron complex catalyst encapsulated in a resin according to any one of Items 1 to 3, wherein the silicone resin has a reactive functional group (e.g., one or more selected from the group consisting of a silanol group, an alkoxy group, a vinyl group, a hexenyl group, an octenyl group, an epoxy group, and a methacryl group).

[0120] [Item 5] The iron complex catalyst encapsulated in a resin according to any one of Items 1 to 4, wherein the silicone resin has at least one of four components represented by the following chemical formulas: T component (T unit, T unit: trifunctional organosilsesquioxane unit), D component (D unit, D unit: difunctional diorganosiloxane unit), M component (M unit, M unit: monofunctional triorganosiloxy unit), and Q component (Q unit, Q unit: tetrafunctional unit), and preferably contains the T component, or the D component and the T component.

[0121] [ka]

[0122] In the formula, R is, independently of each other, an alkyl group (e.g., a methyl group) and / or an aryl group (e.g., a phenyl group).

[0123] [Item 6] The iron complex catalyst encapsulated in a resin according to any one of Items 1 to 5, wherein the silicone resin contains a component T represented by the following formula:

[0124] [ka]

[0125] wherein R are, independently of each other, alkyl and / or aryl groups.

[0126] [Item 7] The iron complex catalyst encapsulated in a resin according to Item 5 or 6, wherein the proportion of the T component to the total components (T component, D component, M component, and Q component) contained in the silicone resin is 70% or more, preferably 70 to 100%, more preferably 85 to 100%, and even more preferably 90 to 100%. The proportions (%) of the T component and the D component are 29 It can be determined by the area ratio of Si-NMR.

[0127] [Item 8] The iron complex catalyst encapsulated in a resin according to any one of Items 5 to 7, wherein the silicone resin contains 0 to 5% of component T1, 10 to 70% of component T2, and 20 to 90% of component T3 relative to the total content of component T. The percentages (%) of component T are: 29 It can be determined by the area ratio of Si-NMR.

[0128] [ka]

[0129] In the formula, R aare, independently of each other, alkyl groups (e.g., methyl groups) and / or aryl groups (e.g., phenyl groups). b are, independently of each other, alkyl groups (e.g., methyl groups, ethyl groups, etc.) and / or hydrogen (H).

[0130] [Item 9] The iron complex catalyst encapsulated in a resin according to any one of Items 5 to 8, wherein the silicone resin contains 0 to 10%, preferably 0 to 5% (total) of the D component relative to the T component. The ratio (%) of the T component and the D component is 29 It can be determined by the area ratio of Si-NMR.

[0131] [Item 10] The iron complex catalyst encapsulated in a resin according to Item 9, wherein the content of component D1 is 10 to 40% and the content of component D2 is 60 to 90% relative to the total content of component D. The proportion (%) of component D is 29 It can be determined by the area ratio of Si-NMR.

[0132] [ka]

[0133] In the formula, R a R is an alkyl group (e.g., a methyl group) and / or an aryl group (e.g., a phenyl group). b is an alkyl group (e.g., a methyl group, an ethyl group, etc.) and / or hydrogen (H).

[0134] [Item 11] The iron complex catalyst is represented by the formula (I): (L 1 )FeX n1 (I) [In the formula (I), n1 is 2 or 3. Each X is independently -SC(=O)CH3 or -OC(=O)R 10 Represents R 10 represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. Two or more of X are -OC(=O)R 10 If R 10They may be linked together to form a ring structure. Also, if n1 is 3, the two Xs together

[0135] [ka]

[0136] (R 10 represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. * represents the bonding position.) where one X is -SC(=O)CH3 or -OC(=O)R 10 (R 10 represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. L 1 represents a tridentate ligand represented by the following general formula (L-1).

[0137] [ka]

[0138] (In formula (L-1), R 1 and R 2 each independently represents a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, or a halogen atom. The Two R's 3 each independently represents an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent. n2 is an integer of 0 to 4. n3 is an integer of 0 to 5. However, R 1 is attached to a carbon atom of the pyridine skeleton. When n2 is an integer between 2 and 4, R 1 The hydrocarbon groups may be linked together to form a cyclic structure. R 2 is attached to a carbon atom of the quinoline skeleton. When n3 is an integer between 2 and 5, R 2 The hydrocarbon groups may be linked to each other to form a cyclic structure.)] 11. The iron complex catalyst encapsulated in a resin according to any one of items 1 to 10, wherein the iron complex catalyst is represented by the formula:

[0139] [Section 12] R 10 The hydrocarbon group in R is an aliphatic hydrocarbon group (e.g., a methyl group (-CH), a t-butyl group (-C(CH)), a trifluoromethyl group (-CF), or an ethylpentyl group (-CH(CH)CH)) or an aromatic hydrocarbon group, preferably an aliphatic hydrocarbon group; 10 Item 12. The iron complex catalyst encapsulated in a resin according to Item 11, wherein the hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms.

[0140] [Section 13] R 10 Item 13. The iron complex catalyst encapsulated in a resin according to Item 11 or 12, wherein the hydrocarbon group in the formula (I) may have a substituent that is one or more selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a silyl group, an amino group, and a methoxy group.

[0141] [Section 14] R 10 Item 14. The iron complex catalyst encapsulated in a resin according to any one of Items 11 to 13, wherein the cyclic structure formed by bonding together is an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, or a heterocycle.

[0142] [Section 15] R 1 and R 2 Item 15. The resin-encapsulated iron complex catalyst according to any one of Items 11 to 14, wherein the halogen atoms in the formula (I) are each independently one or more selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0143] [Section 16] R 1 and R 2are each independently one or more selected from a methyl group (-CH3), an ethyl group (-CH2CH3), an n-propyl group (-CH2CH2CH3), an i-propyl group (-CH(CH3)2), an n-butyl group (-CH2CH2CH2CH3), a t-butyl group (-C(CH3)3), a pentyl group (-CH2(CH2)3CH3), a hexyl group (-CH2(CH2)4CH3), a phenyl group, a 2,6-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,4,6-trimethylphenyl group, a 2,6-diisopropylphenyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0144] [Section 17] R 3 is one or more selected from a methyl group (-CH3), an ethyl group (-CH2CH3), an n-propyl group (-CH2CH2CH3), an i-propyl group (-CH(CH3)2), an n-butyl group (-CH2CH2CH2CH3), a t-butyl group (-C(CH3)3), a pentyl group (-CH2(CH2)3CH3), a hexyl group (-CH2(CH2)4CH3), a heptyl group (-CH2(CH2)5CH3), an octyl group (-CH2(CH2)6CH3), a nonyl group (-CH2(CH2)7CH3), a decyl group (-CH2(CH2)8CH3), a phenyl group, a 2,6-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,4,6-trimethylphenyl group, and a 2,6-diisopropylphenyl group.

[0145] [Item 18] The iron complex catalyst encapsulated in a resin according to any one of Items 11 to 17, wherein in formula (L-1), n2 is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0146] [Item 19] The iron complex catalyst encapsulated in a resin according to any one of Items 11 to 18, wherein in formula (L-1), n3 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

[0147] [Item 20] In the formula (L-1), when n2 is 2, two R 1 Item 20. The iron complex catalyst encapsulated in a resin according to any one of Items 11 to 19, wherein the groups are linked to form a cycloheptane structure, a cycloheptene structure, a cyclohexane structure, or a cyclohexene structure.

[0148] [Item 21] In the formula (L-1), when n3 is an integer of 2 to 5, preferably 2, two R 2 Item 21. The resin-encapsulated iron complex catalyst according to any one of Items 11 to 20, wherein the groups are linked to form a cycloheptane structure, a cycloheptene structure, a cyclohexane structure, or a cyclohexene structure.

[0149] [Item 22] The resin-encapsulated iron complex catalyst according to any one of Items 11 to 21, wherein the metal complex compound represented by general formula (I) is selected from the following:

[0150] [ka]

[0151] [ka]

[0152] [ka]

[0153] [Item 23] The iron complex catalyst encapsulated in a resin according to any one of Items 11 to 22, wherein the metal complex compound represented by general formula (I) is a compound represented by formula (1):

[0154] [ka]

[0155] [Item 24] The iron complex catalyst encapsulated in a resin according to any one of Items 1 to 23, wherein the iron complex catalyst encapsulated in the resin contains 0.001 to 50 mass %, preferably 0.01 to 30 mass %, more preferably 0.1 to 20 mass % of the iron complex catalyst.

[0156] [Item 25] An addition-curable composition comprising an iron complex catalyst encapsulated in the resin according to any one of items 1 to 24.

[0157] [Item 26] The addition-curable composition according to Item 25, further comprising an alkenyl group-containing organopolysiloxane and a SiH group-containing organopolysiloxane.

[0158] [Item 27] ​​The alkenyl group-containing organopolysiloxane has an average unit formula: R'aSiO (4-a) / 2 [wherein R' is a substituted or unsubstituted monovalent hydrocarbon group, preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, the monovalent hydrocarbon group is preferably an alkyl group, an alkenyl group, an aryl group, or an aralkyl group, and the substituent of the substituted monovalent hydrocarbon group is preferably a halogen atom and / or an alkoxy group; a is a number between 1.0 and 2.3, At least two silicon-bonded alkenyl groups in the molecule Item 27. The addition-curable composition according to item 26,

[0159] [Item 28] The addition-curable composition according to Item 26 or 27, wherein the SiH group-containing organopolysiloxane is an organohydrogenpolysiloxane.

[0160] [Item 29] The addition-curable composition according to any one of Items 26 to 28, wherein the amount of the iron complex catalyst encapsulated in the resin is 0.00001 equivalents or more, preferably 0.0001 equivalents or more, and more preferably 0.001 equivalents or more, relative to 1 equivalent of the alkenyl group-containing organopolysiloxane, and is 1 equivalent or less, preferably 0.1 equivalents or less, and more preferably 0.01 equivalents or less.

[0161] [Item 30] A method for hydrosilylation of an alkene by reacting an alkene with a hydrosilane in the presence of the iron complex catalyst encapsulated in the resin according to any one of Items 1 to 24.

[0162] [Item 31] A method for carrying out dehydrogenative coupling of a silane compound by reacting the silane compound with the iron complex catalyst encapsulated in the resin according to any one of Items 1 to 24.

[0163] [Item 32] A method for producing the resin-encapsulated iron complex catalyst according to any one of Items 1 to 24, wherein the iron complex catalyst is obtained by removing the solvent from a mixture of the iron complex catalyst, the resin, and the solvent.

[0164] <Example> The silicone resins used in the examples are as follows: Methyl silicone resin (T1 component (2%), T2 component (21%), T3 component (74%), D1 component (0.8%), D2 component (2.2%). The ratios of T1, T2 and T3 components to the total T components were 1.2%, 21.6% and 76.3%, respectively. The proportion of the total T components was 97.0%. The ratios of these components were 29 Calculated from area ratio by Si-NMR* 1 )

[0165] Phenyl silicone resin (T2 component (62.3%), T3 component (37.7%). The proportion of all T components was 100%. The proportion of these components was 29 Calculated from area ratio by Si-NMR* 1 )

[0166] *1) For the structure of silicone resin, refer to Miyajima et al., Asahi Glass Research Report, 66, p. 32-36 (2016). 29 This was determined by Si-NMR.

[0167] < 29 Si-NMR measurement conditions> Device name: Bruker AVANCEIII400HD Observed nucleus: 29Si Observation frequency: 79.5MHz Measurement temperature: 20℃ Measurement solvent: CDCl3 Pulse width: 9.1μsec (45°) Pulse repetition time: 25.0 seconds Accumulation count: 3000 times Sample concentration (sample / measurement solvent): 200 mg / 0.55 ml

[0168] The structures of the silicone resin components T1, T2, T3, D1, and D2 are as shown below.

[0169] [ka]

[0170] [ka]

[0171] In the above formula, R a are CH3 (methyl silicone resin) and Ph (phenyl silicone resin). R b is CH3 and / or hydrogen (methyl silicone resin), hydrogen (phenyl silicone resin).

[0172] The resin-encapsulated iron complex catalyst was prepared as follows: The iron chloride complex was synthesized according to Kamitani et al., Bull. Chem. Soc. Jpn., 2018, 91, 1429-1435.

[0173] [Manufacturing Example 1] Preparation of iron complex (1) Diethyl ether (50 mL) was added to a mixture of chloride iron complex (1.00 g, 2.14 mmol) and sodium 2-ethylhexanoate (NaEH, 708 mg, 4.26 mmol), and the mixture was stirred at 25 °C (room temperature) for 48 hours. After removing insoluble matter by filtration, the solvent was evaporated from the filtrate by vacuum drying. Hexane (25 mL) was added to the resulting green oil, and the mixture was stirred at room temperature for 30 minutes. The precipitated green solid was filtered, washed twice with hexane (5 mL), and then vacuum dried to obtain iron complex (1) (953 mg, 1.40 mmol, 65%) as a green solid.

[0174] [ka]

[0175] [Example 1] A mixture of iron complex (1) (5.0 mg) and methylsilicone resin (500 mg) was dissolved in benzene (0.5 mL) to prepare a solution. The solvent was removed from the solution by vacuum drying, yielding a powder. The resulting powder was heated to 80°C to melt it, and then cooled to 25°C to produce an iron complex catalyst encapsulated in resin containing 1% by mass of iron complex (1).

[0176] [Example 2] A mixture of iron complex (1) (0.120 g) and methylsilicone resin (1.080 g) was dissolved in benzene (2 mL) to prepare a solution. The solvent was removed from the solution by vacuum drying, yielding a powder. The resulting powder was heated to 80°C to melt it, and then cooled to 25°C to produce an iron complex catalyst encapsulated in resin containing 10% by mass of iron complex (1).

[0177] [Example 3] Iron complex (1) (0.140 g) and phenyl silicone resin (1.260 g) were mixed, and benzene (10 mL) was added to the resulting mixture to prepare a solution. The solvent was removed from the solution by vacuum drying, yielding a powder. The resulting powder was heated to 110°C to melt it, and then cooled to 25°C to produce an iron complex catalyst encapsulated in a resin containing 10% by mass of iron complex (1).

[0178] Table 1 shows the results of the stability evaluation under air atmosphere for Examples 1 to 3 and Comparative Example 1 (iron complex (1) itself).

[0179] [Table 1]

[0180] The stability in an air atmosphere was evaluated by UV-vis measurement of the iron complex catalyst encapsulated in the resin one day and one month after production. If absorption at the maximum absorption wavelength of 748 nm attributable to iron complex (1) was confirmed, the catalyst was judged to be stable, and if absorption was not confirmed, the catalyst was judged to be decomposed. As shown in Table 1, the iron complex catalysts encapsulated in the resins produced in Examples 1 to 3 were stable in an air atmosphere one day and one month later, but the iron complex (1) not encapsulated in the resin in Comparative Example 1 was decomposed.

[0181] [Example 4] Hydrosilylation of alkenes using the resin-encapsulated iron complex catalyst prepared in Example 1

[0182] [ka]

[0183] The resin-encapsulated iron complex catalyst (100 mg, containing 1.0 mg of iron complex (1), containing 0.0001 equivalent of iron complex (1) per equivalent of phenylsilane) prepared in Example 1 and stored in air for at least one day was added to a mixed solution of phenylsilane (1.80 mL) and 1-dodecene (3.25 mL, 1 equivalent per 1.0 equivalent of phenylsilane) under an argon atmosphere. The reaction mixture was stirred at 25°C for 20 hours, and the product was obtained. 1 This was confirmed by H-NMR measurement and GC-MS. As a result, phenylsilane and 1-dodecene were completely consumed, and the hydrosilylated product, PhH2SiC 12 H 25 It was confirmed that the compound was produced in 100% yield.

[0184] [Example 5] Hydrosilylation of alkenes using the resin-encapsulated iron complex catalyst prepared in Example 2 The resin-encapsulated iron complex catalyst (100 mg, containing 10.0 mg of iron complex (1), containing 0.001 equivalent of iron complex (1) per equivalent of phenylsilane) prepared in Example 2 and stored in air for at least one day was added to a mixed solution of phenylsilane (1.80 mL) and 1-dodecene (3.25 mL, 1 equivalent per 1.0 equivalent of phenylsilane) under an argon atmosphere. The reaction mixture was stirred at 25°C for 20 hours, and the product was obtained. 1 This was confirmed by H-NMR measurement and GC-MS. As a result, phenylsilane and 1-dodecene were completely consumed, and the hydrosilylated product, PhH2SiC 12 H 25 It was confirmed that the compound was produced in 100% yield.

[0185] [Example 6] Hydrosilylation of alkenes using the resin-encapsulated iron complex catalyst prepared in Example 3 The resin-encapsulated iron complex catalyst (100 mg, containing 10.0 mg of iron complex (1), containing 0.001 equivalent of iron complex (1) per equivalent of phenylsilane) prepared in Example 3 and stored in air for at least one day was added to a mixed solution of phenylsilane (1.80 mL) and 1-dodecene (3.25 mL, 1 equivalent per 1.0 equivalent of phenylsilane) under an argon atmosphere. The reaction mixture was stirred at 25°C for 20 hours, and the product was obtained. 1 This was confirmed by H-NMR measurement and GC-MS. As a result, phenylsilane and 1-dodecene were completely consumed, and the hydrosilylated product, PhH2SiC 12 H 25 It was confirmed that the compound was produced in 100% yield.

[0186] Comparative Example 2 Hydrosilylation of alkenes using iron complex (1) Iron complex (1) (1.0 mg, containing 0.0001 equivalents of iron complex (1) per equivalent of phenylsilane) that had been stored in air for more than one day was added to a mixed solution of phenylsilane (1.80 mL) and 1-dodecene (3.25 mL, 1 equivalent per 1.0 equivalent of phenylsilane) under an argon atmosphere. The reaction mixture was stirred at 25 °C for 20 hours, and the product was obtained. 1 This was confirmed by H-NMR measurement and GC-MS. The results showed that phenylsilane and 1-dodecene were not completely consumed, and the conversion rate to the hydrosilylated product was less than 70%.

[0187] The results of Examples 4 to 6 confirmed that the iron complex catalyst encapsulated in the resin of the present invention can be used effectively for the hydrosilylation of alkenes even after storage in air for one day or more. It was also confirmed that the hydrosilylation product was similarly produced when iron complex (1) stored under a nitrogen atmosphere was used instead of the iron complex catalyst encapsulated in the resin (see JP 2020-50637 A and M. Kamitani et al., Chem. Lett., 2019, 48, 1196-1198).

[0188] [Example 7] Dehydrogenative coupling of silane compounds using the resin-encapsulated iron complex catalyst prepared in Example 1

[0189] [ka]

[0190] The resin-encapsulated iron complex catalyst (100 mg, containing 1.0 mg of iron complex (1), containing 0.001 equivalent of iron complex (1) per equivalent of phenylsilane) prepared in Example 1 and stored in air for at least one day was added to phenylsilane (0.18 mL) under an argon atmosphere. The reaction mixture was stirred at 25°C for 20 hours, and the product was obtained. 1 This was confirmed by H-NMR measurement, which confirmed that phenylsilane was completely consumed and that polysilane, the dehydrogenative coupling product, was produced in a yield of 58%.

[0191] The results of Example 7 confirmed that the iron complex catalyst encapsulated in the resin of the present invention can be used sufficiently for the dehydrogenative coupling of silane compounds even after storage in air for one day or more. It was also confirmed that a dehydrogenative coupling product was similarly produced when iron complex (1) stored under a nitrogen atmosphere was used instead of the iron complex catalyst encapsulated in the resin.

[0192] [Example 8] Silicone addition curing reaction using the iron complex catalyst encapsulated in the resin prepared in Example 1 A two-component addition-cure silicone polymer that produces a silicone gel upon curing was used. The resin-encapsulated iron complex catalyst (100 mg, containing 1.0 mg of iron complex (1) and 0.4 mg of iron) prepared in Example 1 and stored in air for at least one day was added to a mixed solution of a base polymer (alkenyl group-containing organopolysiloxane, 2.84 g) and an organohydrogenpolysiloxane (crosslinker, SiH group-containing organopolysiloxane, 1.16 g; Si-H groups in the SiH group-containing organopolysiloxane / alkenyl groups in the alkenyl group-containing organopolysiloxane (equivalent ratio) = 1:1) and mixed uniformly. The reaction mixture was heated at 80°C for 3 hours to obtain a cured product.

[0193] The results of Example 8 confirmed that the iron complex catalyst encapsulated in the resin of the present invention can be fully used in silicone addition curing reactions even after storage in air for one day or more.

[0194] The iron complex catalyst encapsulated in the resin of the present invention is easy to handle and store, since the iron complex catalyst is unstable in air and does not need to be handled under an inert atmosphere.

Claims

1. An iron complex catalyst encapsulated in a resin, The iron complex catalyst is a catalyst for the hydrosilylation reaction of alkenes, a catalyst for the dehydrogenation coupling reaction of silanes, or a catalyst for the addition-curing reaction of silicones. The iron complex catalyst is given by formula (I): (L 1 )FeX n1 (I) [In the above formula (I), n1 is either 2 or 3. Each X independently represents -SC(=O)CH3 or -OC(=O)R10. R10 represents a C1-C12 hydrocarbon group which may have substituents. If two or more of X are -OC(=O)R10, the R10s may be linked together to form a ring structure. Also, if n1 is 3, the two X's become 【Chemistry 29】 (R 10 represents a hydrocarbon group having 1 to 12 carbon atoms, which may have substituents. * indicates the bond position.) This represents a hydrocarbon group having 1 to 12 carbon atoms, where one X may be -SC(=O)CH3 or -OC(=O)R10 (where R10 represents a hydrocarbon group having 1 to 12 carbon atoms, which may have substituents). L1 represents a tridentate ligand shown by the following general formula (L-1). 【Transformation 30】 (In formula (L-1), R1 and R2 each independently represent a C1-C6 hydrocarbon group which may have substituents, a C6-C12 aromatic hydrocarbon group which may have substituents, or a halogen atom. Each of the two R3s independently represents an alkyl group having 1 to 12 carbon atoms that may have substituents, or an aromatic hydrocarbon group having 6 to 12 carbon atoms that may have substituents. n² is an integer between 0 and 4. n3 is an integer between 0 and 5. However, R1 is bonded to a carbon atom of the pyridine skeleton. If n2 is an integer between 2 and 4, the hydrocarbon groups of R1 may be linked together to form a cyclic structure. R2 bonds to a carbon atom in the quinoline skeleton. If n3 is an integer between 2 and 5, the hydrocarbon groups of R2 may be linked together to form a cyclic structure. An iron complex catalyst encapsulated in resin, represented as shown.

2. The resin comprises a silicone resin that is solid at room temperature, wherein the iron complex catalyst is encapsulated in the resin according to claim 1.

3. The iron complex catalyst encapsulated in the resin according to claim 2, wherein the silicone resin is one or more selected from the group consisting of methyl silicone resin, phenyl silicone resin, and methylphenyl silicone resin.

4. The aforementioned silicone resin contains component T, which is represented by the following formula: 【Chemistry 31】 (Here, R is independently an alkyl group and / or an aryl group.) The iron complex catalyst encapsulated in the resin according to claim 2, wherein the ratio of component T to the total components contained in the silicone resin is 70% or more.

5. The iron complex catalyst encapsulated in the resin according to Claim 1, wherein the iron complex catalyst encapsulated in the resin comprises 0.001 to 50% by mass of the iron complex catalyst.

6. An addition-curing composition comprising an iron complex catalyst encapsulated in the resin according to Claim 1.

7. The addition-curing composition according to claim 6, further comprising an alkenyl group-containing organopolysiloxane and an SiH group-containing organopolysiloxane.

8. The addition-curing composition according to claim 7, wherein the amount of iron complex catalyst encapsulated in the resin is 0.00001 equivalents or more and 1 equivalent or less per equivalent of the alkenyl group-containing organopolysiloxane.

9. A method for carrying out an addition-curing reaction between an alkenyl group-containing organopolysiloxane and an SiH group-containing organopolysiloxane, wherein a cured product is obtained by heating the addition-curing composition described in Claim 7.

10. A method for obtaining a cured product by applying a solvent to an alkenyl group-containing organopolysiloxane, an SiH group-containing organopolysiloxane, and an iron complex catalyst encapsulated in the resin according to any one of claims 1 to 5, thereby generating an iron complex catalyst, and causing a reaction between the alkenyl group-containing organopolysiloxane and the SiH group-containing organopolysiloxane.

11. A method for hydrosilylation of an alkene by reacting an alkene with a hydrosilane in the presence of an iron complex catalyst encapsulated in a resin according to any one of claims 1 to 5.

12. A method for performing dehydrogenation coupling of a silane compound by reacting the silane compound with an iron complex catalyst encapsulated in a resin according to any one of claims 1 to 5.

13. A method for producing an iron complex catalyst encapsulated in a resin, according to claim 1, wherein the iron complex catalyst encapsulated in the resin is obtained by removing the solvent from a mixture of the iron complex catalyst, the resin, and the solvent.

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