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

Abstract

Provided are: an iron complex catalyst encapsulated in a resin, the iron complex catalyst capable of eliminating the need to handle and store, in the inert atmosphere, an iron complex catalyst unstable in the air; an addition-curable composition containing the same; and a method for producing the same. The iron complex catalyst encapsulated in a resin is a catalyst for a hydrosilylation reaction of alkene or a catalyst for a dehydrogenation coupling reaction of silane. The addition-curable composition contains the iron complex catalyst encapsulated in a resin. The method for producing an iron complex catalyst encapsulated in a resin comprises a step for removing a solvent from a mixture of an iron complex catalyst, a resin, and the solvent to obtain the iron complex catalyst encapsulated in a resin.

Description

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

[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.

[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]

[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 Publication 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 silanes, which also primarily uses transition metal catalysts (see JP-A-6-145360 and JP-A-2010-47699).

[0007] The present invention relates to a resin-encapsulated iron complex catalyst, wherein the iron complex catalyst is a catalyst for a hydrosilylation reaction of an alkene, a catalyst for a dehydrocoupling reaction of a silane, or a catalyst for a silicone addition curing reaction. Detailed Description of the Invention

[0008] In developing various iron complex catalysts for the synthesis of the organosilicon compounds, the present inventors have developed iron complex catalysts that satisfy requirements such as high reaction conversion rates, fast reaction rates, and a wide range of applicable substrates (see JP 2020-117474 A). However, such iron complex catalysts are unstable in air and therefore require storage 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, in an inert atmosphere, and an addition-curable composition containing the same.

[0010] The present invention relates to a resin-encapsulated iron complex catalyst, wherein the iron complex catalyst is a catalyst for a hydrosilylation reaction of an alkene, a catalyst for a dehydrocoupling reaction of a silane, or a catalyst for a silicone addition curing reaction.

[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 a Resin> The present invention relates to 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 refers to 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 a combination of both is preferred. These silicone resins may have a reactive functional group (such as a silanol group, an alkoxy group, a vinyl group, a hexenyl group, an octenyl group, an epoxy group, or a methacrylic group).

[0019] The silicone resin has at least one of four components represented by the following chemical formula: 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. Examples of such silicone resins include T resins consisting of only the T component, MTQ resins containing a combination of the M component, T component, and Q component, MDTQ resins containing a combination of the M component, D component, T component, and Q component, DT resins containing a combination of the D component and T component, and TDQ resins containing a combination of the D component, T component, and Q component. Preferred examples of such silicone resins include T resins and DT resins.

[0020]

[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 of the components contained in the silicone resin (the T component, the D component, the M component, and the 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] In addition, the T component of the silicone resin specifically includes at least one of the structures shown below: T0 component, T1 component, T2 component, and T3 component.

[0024]

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

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

[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]

[0029] In the formula, R a 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 silicone addition curing reaction. 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)CH or —OC(═O)R 10 Represents R 10 represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. 10 If R 10 When n1 is 3, two Xs may be linked together to form a ring structure.

[0035]

[0036] (R 10 represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. * represents a bonding position.) and 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. 1 represents a tridentate ligand represented by the following general formula (L-1).

[0037]

[0038] [In formula (L-1), R 1 and R 2each 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. 3 are each independently 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 bonded to a carbon atom of the pyridine skeleton. When n2 is an integer of 2 to 4, R 1 The hydrocarbon groups may be linked together to form a cyclic structure. 2 is bonded to a carbon atom of the quinoline skeleton. When n3 is an integer of 2 to 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)CH or —OC(═O)R 10 Represents R 10 represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. 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 formula (I), L 1 represents a tridentate ligand represented by general formula (L-1). 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 R 2 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 2Examples 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 is 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 bonded to a carbon atom of the pyridine skeleton. 1 is bonded to a carbon atom of the pyridine skeleton, the state in which R is bonded to a carbon atom constituting 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 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 bonded to a carbon atom of the quinoline skeleton. 2 is bonded to a carbon atom of the quinoline skeleton, the carbon atom constituting the quinoline ring is bonded to a carbon atom of the quinoline skeleton. 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 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]

[0064]

[0065]

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

[0067]

[0068] The iron complex catalyst can be produced, for example, according to the methods described in the following documents: JP 2020-117474 A; 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. al, Organometallics, 2023, 42, 1839-1848.

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

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

[0071] <<Mixture of Iron Complex Catalyst, Resin, and Solvent>> The mixture of iron complex catalyst, resin, and solvent can be obtained by adding the iron complex catalyst and 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 dehydrogenative coupling reaction of a silane, or a catalyst for the silicone addition curing reaction, and can be produced according to known literature or obtained commercially.

[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 a Mixture of Iron Complex Catalyst, Resin, and Solvent>> Methods for removing the solvent from a mixture of iron complex catalyst, resin, and 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 necessary, 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 the iron complex catalyst encapsulated in the resin of the present invention. The hydrosilylation of the alkene produces an organosilicon compound.

[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] <<Alkenes>> Examples of the alkenes include compounds represented by the following formula (II).

[0080]

[0081] In the formula (II), R 21 , R 22 , R 23 and R 24 each 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] <<Hydrosilane>> Examples of the hydrosilane include compounds represented by the following formula (III).

[0084]

[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] <<Amounts 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 alkenes 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] <<Use Amount of Iron Complex Catalyst Encapsulated in Resin>> The use amount of the iron complex catalyst encapsulated in the resin can be appropriately selected depending on the purpose. For example, the use amount (the use 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 use amount 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 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.

[0090] <<Reaction Temperature, Reaction Time>> 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. If the reaction temperature is within the above range, the organosilicon compound 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 Compound> 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. The dehydrogenative coupling 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 Compound>> Examples of the silane compound include compounds represented by the following formula (IV).

[0096]

[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] <<Use Amount of Iron Complex Catalyst Encapsulated in Resin>> The use amount of the iron complex catalyst encapsulated in the resin can be appropriately selected depending on the purpose. For example, the use amount (the use 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 facilitated, and the silane polymer can be produced with a higher yield. The above-mentioned resin-covered 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 use amount is within the above range.

[0100] <<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, the silane compound 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.

[0101] <<Reaction Temperature, Reaction Time>> 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. If the reaction temperature is within the above range, polysilane can be produced in a higher yield.

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

[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 the resin of the present invention. Such an addition-curable composition containing an iron complex catalyst encapsulated in the 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 be, for example, 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 from 1.0 to 2.3, and the compound has at least two silicon-bonded alkenyl groups in the molecule.

[0107] 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, and an aralkyl group. Examples of the substituent of the substituted monovalent hydrocarbon group include a halogen atom and an alkoxy group. a is a number from 1.0 to 2.3.

[0108] <<SiH Group-Containing Organopolysiloxane (Crosslinking Component)>> Examples of SiH group-containing organopolysiloxanes include organohydrogenpolysiloxanes. SiH group-containing organopolysiloxanes function as crosslinking components, and a cured product is formed by addition reaction (hydrosilylation) between the SiH groups in this component and the alkenyl groups in the alkenyl group-containing organopolysiloxane. Any SiH group-containing organopolysiloxane can be used as a crosslinking component as long as it has two or more hydrogen atoms bonded to silicon atoms (i.e., SiH groups) per molecule. The molecular structure of this SiH group-containing organopolysiloxane may be linear, cyclic, branched, or a three-dimensional network structure. Furthermore, SiH group-containing organopolysiloxanes having a number of silicon atoms per molecule (i.e., degree of polymerization) of 2 to 1000, particularly about 2 to 300, are preferably used as crosslinking components.

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

[0110] <<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 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 alkenyl group-containing organopolysiloxane, 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 a cured product can be produced with a higher 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 involve the use of a solvent, but can be suitably carried out without a solvent. When no solvent is used, for example, the crosslinking component may also serve 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. If the reaction temperature is within the above range, the silane polymer can be produced in a higher yield.

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

[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, wherein the iron complex catalyst is a catalyst for a hydrosilylation reaction of an alkene, a catalyst for a dehydrogenative coupling reaction of a silane, or a catalyst for a silicone addition curing reaction.

[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: a T component (T units, T units: trifunctional organosilsesquioxane units), a D component (D units, D units: difunctional diorganosiloxane units), an M component (M units, M units: monofunctional triorganosiloxy units), and a Q component (Q units, Q units: tetrafunctional units), and preferably contains the T component, or both the D component and the T component.

[0121]

[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 resin-encapsulated iron complex catalyst according to any one of Items 1 to 5, wherein the silicone resin contains a T component represented by the following formula:

[0124]

[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 has a T1 component content of 0 to 5%, a T2 component content of 10 to 70%, and a T3 component content of 20 to 90% relative to the total T component. The percentages (%) of the T components are: 29 It can be determined by the area ratio of Si-NMR.

[0128]

[0129] In the formula, R a are each independently an alkyl group (e.g., a methyl group) and / or an aryl group (e.g., a phenyl group). b are each independently an alkyl group (e.g., a methyl group, an ethyl group, 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%, of the D component (total) 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]

[0133] In the formula, R a 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. 10 If R 10 When n1 is 3, two Xs may be linked together to form a ring structure.

[0135]

[0136] (R 10 represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. * represents a bonding position.) and 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. 1 represents a tridentate ligand represented by the following general formula (L-1).

[0137]

[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. 3are each independently 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 bonded to a carbon atom of the pyridine skeleton. When n2 is an integer of 2 to 4, R 1 The hydrocarbon groups may be linked together to form a cyclic structure. 2 is bonded to a carbon atom of the quinoline skeleton. When n3 is an integer of 2 to 5, R 2 11. The iron complex catalyst encapsulated in a resin according to any one of items 1 to 10, wherein the hydrocarbon groups may be linked to each other to form a cyclic structure.

[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 2Item 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 2 are each independently one or more selected from the group consisting of 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 Item 17. The iron complex catalyst encapsulated in a resin according to any one of Items 11 to 16, wherein R is one or more selected from the group consisting of 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] In formula (L-1), n2 is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0. The iron complex catalyst encapsulated in a resin according to any one of Items 11 to 17.

[0146] [Item 19] 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. The iron complex catalyst encapsulated in a resin according to any one of Items 11 to 18.

[0147] [Item 20] In the formula (L-1), when n2 is 2, two R 1 Item 20. The resin-encapsulated iron complex catalyst 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 following 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]

[0151]

[0152]

[0153] [Item 23] The resin-encapsulated iron complex catalyst 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]

[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 the average unit formula: R'aSiO (4-a) / 2 Item 27. The addition-curable composition according to Item 26, represented by the formula: [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, the substituent of the substituted monovalent hydrocarbon group is preferably a halogen atom and / or an alkoxy group, a is a number from 1.0 to 2.3, and at least two silicon-bonded alkenyl groups are present in the molecule].

[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 a resin-encapsulated iron complex catalyst according to any one of Items 1 to 24, wherein the resin-encapsulated iron complex catalyst is obtained by removing the solvent from a mixture of the iron complex catalyst, the resin, and the solvent.

[0164] <Examples> 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 the 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 the area ratio by Si-NMR* 1 )

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

[0167] < 29 Si-NMR measurement conditions> Device name: AVANCEIII400HD manufactured by Bruker Observation nucleus: 29Si Observation frequency: 79.5 MHz Measurement temperature: 20°C Measurement solvent: CDCl3 Pulse width: 9.1 μsec (45°) Pulse repetition time: 25.0 sec Number of accumulations: 3000 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]

[0170]

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

[0172] The resin-encapsulated iron complex catalyst was produced by the following method: The iron chloride complex was synthesized according to Kamitani et al., Bull. Chem. Soc. Jpn., 2018, 91, 1429-1435.

[0173] [Production Example 1] Production 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 distilled off from the filtrate by vacuum drying. Hexane (25 mL) was added to the resulting green oily substance, and the mixture was stirred at room temperature for 30 minutes. The precipitated green solid was filtered off, 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]

[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 obtained powder was heated to 80°C to melt it, and then cooled to 25°C to produce an iron complex catalyst in which 1% by mass of iron complex (1) was encapsulated in a resin.

[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 to obtain a powder. The obtained powder was heated to 80°C to melt it, and then cooled to 25°C to produce an iron complex catalyst in which 10% by mass of iron complex (1) was encapsulated in a resin.

[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 in which 10% by mass of iron complex (1) was encapsulated in a resin.

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

[0179]

[0180] The stability in an air atmosphere was evaluated by performing 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 of Comparative Example 1 was decomposed.

[0181] Example 4 Hydrosilylation of Alkenes Using the Resin-Encapsulated Iron Complex Catalyst Prepared in Example 1

[0182]

[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) produced 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 hydrosilylation product PhHSiC 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 1 This was confirmed by H-NMR measurement and GC-MS. As a result, phenylsilane and 1-dodecene were completely consumed, and the hydrosilylation product PhHSiC 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 1 This was confirmed by H-NMR measurement and GC-MS. As a result, phenylsilane and 1-dodecene were completely consumed, and the hydrosilylation product PhHSiC 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 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 1The results were confirmed by H-NMR measurement and GC-MS, and it was found that phenylsilane and 1-dodecene were not completely consumed, and the conversion rate to the hydrosilylated product was 70% or less.

[0187] The results of Examples 4 to 6 confirmed that the iron complex catalyst encapsulated in the resin of the present invention can be satisfactorily used for the hydrosilylation of alkenes even after storage in air for one day or more. It was also confirmed that a hydrosilylated 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 Dehydrocoupling of silane compounds using the resin-encapsulated iron complex catalyst prepared in Example 1

[0189]

[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, and the results confirmed that phenylsilane was completely consumed and 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 satisfactorily 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 Cure Reaction Using the Resin-Encapsulated Iron Complex Catalyst Produced 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) produced 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 (crosslinking agent, SiH group-containing organopolysiloxane, 1.16 g; equivalent ratio of Si—H groups in the SiH group-containing organopolysiloxane to alkenyl groups in the alkenyl group-containing organopolysiloxane = 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. A resin-encapsulated iron complex catalyst, wherein 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 addition curing reaction of a silicone.

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

3. The resin-encapsulated iron complex catalyst according to claim 2, wherein the silicone resin is at least one selected from the group consisting of methylsilicone resin, phenylsilicone resin, and methylphenylsilicone resin.

4. The silicone resin contains a T component represented by the following formula: (wherein R is, independently of each other, an alkyl group and / or an aryl group). The iron complex catalyst encapsulated in a resin according to claim 2 or 3, wherein the ratio of component T to all components contained in the silicone resin is 70% or more.

5. The iron complex catalyst is represented by the formula (I): 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. 10 If R 10 When n1 is 3, two Xs may be linked together to form a ring structure. (R 10 represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. * represents a bonding position.) and 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. 1 represents a tridentate ligand represented by the following general formula (L-1). (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. 3 are each independently 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 from 2 to 4, R 1 The hydrocarbon groups may be linked together to form a cyclic structure. 2 is attached to a carbon atom of the quinoline skeleton. When n3 is an integer from 2 to 5, R 2 The iron complex catalyst encapsulated in a resin according to any one of claims 1 to 4, represented by the formula (I): wherein the hydrocarbon groups may be linked to each other to form a cyclic structure.

6. An addition-curable composition comprising an iron complex catalyst encapsulated in the resin according to any one of claims 1 to 5.

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

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

9. 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 claims 1 to 5.

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

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