Method for producing ruthenium nanoparticle catalyst, method for producing silyl group-containing compound, and silyl group-containing compound

Abstract

To provide a method for producing a silyl group-containing compound that enables efficient introduction of a silyl group irrespective of the molecular weight of an allyl group-containing compound.SOLUTION: A ruthenium nanoparticle catalyst (A) having a ligand (B) is used as a hydrosilylation reaction catalyst. Alternatively, a hydrosilylation reaction catalyst is constituted by mixing a ruthenium nanoparticle catalyst precursor (A') not having the ligand (B) as a ligand, with the ligand (B). The ligand (B) has at least one carbon-carbon double bond in one molecule, and at least one of the carbon atoms forming the carbon-carbon double bond has a halogen group bonded thereto.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing ruthenium nanoparticle catalysts, a method for producing silyl group-containing compounds, and silyl group-containing compounds.

Background Art

[0002] Organic polymers having a silicon atom, particularly those having a hydroxyl group or a hydrolyzable group on the silicon atom and a silyl group (hereinafter referred to as "hydrolyzable silyl group") capable of forming a siloxane bond, are known as moisture-reactive polymers. Since these polymers are cured by a hydrolysis reaction to form a rubbery cured product having flexibility, they are used in many industrial products such as sealing materials, adhesives, coating materials, paints, and adhesives.

[0003] As a means for obtaining such a silyl group-containing organic polymer, a method of subjecting an allyl group-containing organic polymer and a hydrosilane compound to a hydrosilylation reaction in the presence of a metal catalyst has been adopted. However, it is known that side reactions such as isomerization to a 1-propenyl group (internal olefin) and hydrogenation occur during the reaction. Specifically, in this reaction, the Karstedt catalyst (platinum divinyldisiloxane complex) is widely used, and since about 20% of the above side reactions proceed, there is a limitation on the introduction rate of the silyl group. As a result, the rubbery cured product obtained by curing the curable composition containing the hydrolyzable silyl group-containing organic polymer had room for improvement in its modulus, tensile strength, etc.

[0004] On the other hand, in addition to platinum catalysts such as Karstedt catalysts, metal catalysts that exhibit good activity in hydrosilylation are known, and one of them is a ruthenium catalyst. In Patent Document 1, it has been reported that by reacting an allyl ether compound with a hydrosilane compound in the presence of a specific ruthenium complex, the corresponding silylated product can be efficiently produced. However, when the allyl ether compound has a high molecular weight, the side reaction rate increases and the selectivity of the silylated product decreases, so it has been limited to the production of silylated products with a molecular weight of 3,000 or less. Furthermore, when the amount of the catalyst used is small, the reactivity is not sufficient, and there are problems such as a long production time especially when producing on an industrial scale.

[0005] In addition, metal nanoparticle catalysts are known as metal catalysts that exhibit activity in hydrosilylation. For example, a method for producing an organosilicon compound using a platinum nanoparticle catalyst or a mixed catalyst of a platinum nanoparticle catalyst and an iron nanoparticle catalyst, or only iron element-containing nanoparticles has been disclosed (Patent Documents 2 and 3). Also, a method for producing an organosilicon compound using ruthenium nanoparticles has been disclosed (Patent Document 4). However, in the hydrosilylation reaction of an allyl group-containing compound and a hydrosilane compound, when these catalysts are used, when the allyl group-containing compound has a high molecular weight, the side reaction rate increases and it has been difficult to improve the silylation rate.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0007] The present invention provides a ruthenium nanoparticle catalyst capable of efficiently introducing a silyl group at the terminal when producing a silyl group-containing compound having a number average molecular weight of more than 3,000 by a hydrosilylation reaction, a method for producing the same, a silyl group-containing compound having a number average molecular weight of more than 3,000 and 85% or more of the terminals silylated, and a method for producing the same.

Means for Solving the Problems

[0008] As a result of intensive studies, the present inventors have produced a ruthenium nanoparticle catalyst having a specific compound as a ligand, and in the presence thereof, by performing a hydrosilylation reaction of an allyl group-containing compound, it has been found that a silylated product can be efficiently produced regardless of the molecular weight of the allyl group-containing compound.

[0009] That is, the present invention is A method for producing a ruthenium nanoparticle catalyst (A) used as a hydrosilylation catalyst when producing a silyl group-containing compound (E) having a number average molecular weight of more than 3,000 and a terminal silylation rate of 85% or more, Step 1 of producing a ruthenium nanoparticle catalyst precursor (A') by heating a ruthenium compound (A'') in an organic solvent at 50 to 250 °C; and Step 2 of producing a ruthenium nanoparticle catalyst (A) by coordinating a ligand (B) having a benzene ring skeleton or a norbornadiene skeleton and having at least one halogeno group selected from the group consisting of a fluoro group, a bromo group, and an iodo group bonded to at least one of the carbon atoms in the skeleton to the ruthenium nanoparticle catalyst precursor (A'). Further, the present invention is a method for producing a silyl group-containing compound (E) having a number average molecular weight of more than 3,000 and a terminal silylation rate of 85% or more, using a ruthenium nanoparticle catalyst (A) as a hydrosilylation catalyst, comprising: Step 1 of heating a ruthenium compound (A'') in an organic solvent at 50 to 250 °C to prepare a ruthenium nanoparticle catalyst precursor (A'); Step 2 of producing a ruthenium nanoparticle catalyst (A) by coordinating a ruthenium nanoparticle catalyst precursor (A') and a ligand (B) having a benzene ring skeleton or a norbornadiene skeleton, with at least one halogeno group selected from the group consisting of a fluoro group, a bromo group, and an iodo group bonded to at least one carbon atom in the skeleton; and Step 3 of mixing the ruthenium nanoparticle catalyst (A), an allyl group-containing compound (C), and a hydrosilane compound (D) and subjecting them to hydrosilylation; The present invention relates to a production method including this. Furthermore, the present invention is a method for producing a silyl group-containing compound (E) having a number average molecular weight of more than 3,000 and a terminal silylation rate of 85% or more, using a ruthenium nanoparticle catalyst (A) as a hydrosilylation catalyst, Step 1 of heating a ruthenium compound (A'') in an organic solvent at 50 to 250°C to prepare a ruthenium nanoparticle catalyst precursor (A'); and Step 3' of mixing a ruthenium nanoparticle catalyst precursor (A'), a ligand (B) having a benzene ring skeleton or a norbornadiene skeleton, with at least one halogeno group selected from the group consisting of a fluoro group, a bromo group, and an iodo group bonded to at least one carbon atom in the skeleton, an allyl group-containing compound (C), and a hydrosilane compound (D) and subjecting them to hydrosilylation; The present invention relates to a production method including this. Furthermore, the present invention also relates to a silyl group-containing compound (E) produced by using these production methods, having a number average molecular weight of more than 3,000 and a terminal silylation rate of 85% or more.

Effects of the Invention

[0010] According to the present invention, when producing a silyl group-containing compound having a number average molecular weight of more than 3,000 and a terminal silylation rate of 85% or more, a method for producing a ruthenium nanoparticle catalyst that can be used as a hydrosilylation catalyst can be provided. Further, according to the present invention, a method for producing a silyl group-containing compound capable of introducing a silyl group with high efficiency during the hydrosilylation reaction of an allyl group-containing compound and a hydrosilane compound can be provided. Also, according to the method of the present invention, a general-purpose ruthenium compound can be used as a raw material for the ruthenium nanoparticle catalyst. Furthermore, since the hydrosilylation reaction can proceed efficiently with a small amount of ruthenium catalyst, the production method of the present invention is industrially useful. In addition, the silyl group-containing compound produced by the production method of the present invention has a high probability of silylation at the terminal, and the conversion to an unintended terminal group is suppressed, so it exhibits excellent physical properties such as higher hardness and higher durability than conventional silyl group-containing compounds.

Embodiments for Carrying Out the Invention

[0011] Hereinafter, embodiments of the present invention will be described in detail.

[0012] <Ruthenium Nanoparticle Catalyst (A)> In the present invention, a ruthenium compound (A'') is heated in an organic solvent at 50 to 250 °C to prepare a ruthenium nanoparticle catalyst precursor (A'), and further, the ruthenium nanoparticle catalyst (A) obtained by coordinating a ligand (B) to the ruthenium nanoparticle catalyst precursor (A') can be used.

[0013] When the ruthenium compound (A'') is heated in a coordinating organic solvent, the resulting ruthenium nanoparticle catalyst precursor (A') and ruthenium nanoparticle catalyst (A) can have the coordinating organic solvent coordinated thereto. Examples of the coordinating organic solvent that can be used in the present invention include amide solvents such as N,N-dimethylacetamide (DMA), N,N-dimethylformamide (DMF), and N-methyl-2-pyrrolidone (NMP); sulfoxide solvents such as dimethyl sulfoxide (DMSO); ether solvents such as 1,4-dioxane, diglyme, and tetrahydrofuran (THF); alcohol solvents such as ethylene glycol and propylene glycol; and the like. Among these, DMF is particularly preferred because it acts as a coordinating organic solvent, a reaction solvent, and a reducing agent in the production of the ruthenium nanoparticle catalyst precursor (A') having the coordinating organic solvent coordinated on the surface, and can be produced in one step.

[0014] The particle size (median diameter) of the ruthenium nanoparticle catalyst (A) can be measured by a transmission electron microscope (TEM) and can be adjusted to a range of 0.3 nm or more and 200 nm or less.

[0015] <Ligand (B)> Examples of the ligand (B) that can be used in the present invention include a norbornadiene skeleton, a cyclooctadiene skeleton, a benzene ring skeleton, a benzoquinone skeleton, and the like. More specifically, a 2,5-norbornadiene skeleton, a 1,5-cyclooctadiene skeleton, a p-cymene skeleton, a mesitylene skeleton, a benzene ring skeleton, a benzoquinone skeleton, and the like can be mentioned. Preferably, it has a norbornadiene skeleton or a benzene ring skeleton. Furthermore, the ligand (B) may have 1 to 6 halogeno groups in one molecule, and it is particularly preferable to have 2 or 3 halogeno groups. Examples of the halogeno group include a fluoro group, a chloro group, a bromo group, or an iodo group. When a plurality of halogeno groups are present in the same molecule, they may all be of the same type or may be of different types.

[0016] More specifically, the ligand (B) is, for example, 2-bromonorbornadiene, 2,3-dibromonorbornadiene, 1,4-dibromobenzene, 1,3,5-tribromobenzene, 1,2,4,5-tetrabromobenzene, hexabromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-3,5-dichlorobenzene, 1-bromo-3-chloro-5-fluorobenzene, 1,4-diiodobenzene, 1,3,5-triiodobenzene, 1,2,4,5-tetraiodobenzene, hexaiodobenzene, 1,3-difluoro-5-iodobenzene, 1,3-dichloro-5-iodobenzene, 1,3-dibromo-5-iodobenzene, 1-chloro-3-fluoro-5-iodobenzene, 1-bromo-3-chloro-5-iodobenzene, 1-bromo-3-fluoro-5-iodobenzene, and structural isomers thereof. Among them, from the viewpoint of suppressing by-products, 2,3-dibromonorbornadiene and 1,3,5-tribromobenzene are particularly preferred. From the viewpoint of availability of raw materials during industrial production, ligands having a benzene ring skeleton are preferred.

[0017] Further, the ruthenium nanoparticle catalyst (A) of the present invention may have a ligand (B') that can coordinate to the ruthenium nanoparticle catalyst (A) together with the ligand (B). Examples of the ligand (B') include the above-mentioned coordinating organic solvents, 2,5-norbornadiene ligand, 1,5-cyclooctadiene ligand, p-cymene ligand, mesitylene ligand, benzene ligand, carbonyl ligand, isocyanide ligand, arene ligand, and the like. The ligand (B') is a compound that does not contain the halogeno group described above.

[0018] When the ruthenium nanoparticle catalyst (A) has both the ligand (B) and the ligand (B'), the higher the proportion of the ligand (B) among all the ligands possessed by the ruthenium nanoparticle catalyst (A), the more favorable selectivity can be provided, which is preferable. The proportion of the ligand (B) among all the ligands is preferably 1 to 100% mol, more preferably 50 to 100 mol%.

[0019] The ruthenium nanoparticle catalyst (A) having the ligand (B) can also be obtained by adding the ligand (B) to a system in which the ruthenium nanoparticle catalyst (A') having no ligand (B) exists and converting the ruthenium nanoparticle catalyst precursor (A') into the ruthenium nanoparticle catalyst (A) by the method described below.

[0020] <Allyl group-containing compound (C)> The allyl group-containing compound (C) according to the present embodiment has an allyl group (CH 2 =CH-CH 2 -), and is not particularly limited as long as it can form a silyl group-containing compound (E) by a hydrosilylation reaction with a hydrosilane compound (D). Similar to the silyl group-containing organic polymer (E a ), the allyl group-containing compound (C) may be an allyl group-containing organic polymer. Since the polymer skeleton of the allyl group-containing organic polymer is the same as that of the silyl group-containing organic polymer (E a ), the description thereof will be omitted.

[0021] <Hydrosilane compound (D)> The hydrosilane compound (D) according to the present embodiment is not particularly limited, but preferably has a structure represented by the formula (1). SiR a X b H 4-a-b Formula (1)

[0022] In the general formula (1), R represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. When the general formula (1) contains a plurality of Rs, they may be the same as or different from each other. The hydrocarbon group may be either saturated or unsaturated, and may be any of aliphatic, alicyclic, and aromatic. The number of carbon atoms of the hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. When the hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include halogeno groups such as chloro group, alkoxy groups such as methoxy group, and amino groups such as N,N-diethylamino group.

[0023] Examples of R include unsubstituted alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-hexyl group, 2-ethylhexyl group, n-dodecyl group; substituted alkyl groups such as chloromethyl group, methoxymethyl group, N,N-diethylaminomethyl group; unsaturated hydrocarbon groups such as vinyl group, isopropenyl group, allyl group; cycloalkyl groups such as cyclohexyl group; aryl groups such as phenyl group, toluyl group, 1-naphthyl group; aralkyl groups such as benzyl group and the like. Preferably, it is a substituted or unsubstituted alkyl group, more preferably a methyl group, ethyl group, chloromethyl group, or methoxymethyl group, still more preferably a methyl group or methoxymethyl group, and particularly preferably a methyl group. When a plurality of Rs are present, they may be the same as or different from each other.

[0024] In the general formula (1), X represents a hydroxyl group or a hydrolyzable group. When a plurality of Xs are included in the general formula (1), they may be the same as or different from each other. The hydrolyzable group is not particularly limited and may be a known hydrolyzable group. Examples thereof include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy group and the like. Among these, an alkoxy group, an acyloxy group, a ketoximate group, and an alkenyloxy group are preferable. From the viewpoint of gentle hydrolysis and easy handling, an alkoxy group is more preferable, a methoxy group and an ethoxy group are still more preferable, and a methoxy group is particularly preferable. When a plurality of Xs are present, they may be the same as or different from each other.

[0025] In the general formula (1), a represents any one of 0, 1, 2, and 3, and b represents any one of 0, 1, 2, and 3. a + b is 3 or less, and preferably 3. When the silyl group is a hydrolyzable silyl group, b represents any one of 1, 2, and 3, and from the viewpoint of curability, it is preferably 2 or 3.

[0026] Specific examples of such hydrosilane compounds (D) include, for example, trimethoxysilane, triethoxysilane, triphenoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, (methoxymethyl)dimethoxysilane, (methoxymethyl)diethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, diphenoxymethylsilane, methylsilane, dimethylsilane, trimethylsilane, ethylsilane, diethylsilane, triethylsilane, methyldiethylsilane, dimethylethylsilane, chlorodimethylsilane, dichloromethylsilane, phenylsilane, diphenylsilane, triphenylsilane, phenylmethylsilane, phenyldimethylsilane, diphenylmethylsilane, ethylphenylsilane, diethylphenylsilane, ethyldiphenylsilane, and the like.

[0027] <Silyl group-containing compound (E)> The silyl group-containing compound (E) according to this embodiment is not particularly limited in its specific structure as long as it is a compound in which a trimethylene group derived from the allyl group-containing compound (C) is bonded to a silicon atom derived from the hydrosilane compound (D). The silyl group-containing compound (E) has a silyl group represented by the following general formula (2). -SiR a X b Formula (2)

[0028] R, X, a, and b in the general formula (2) are as described above with respect to the general formula (1).

[0029] The number average molecular weight of the silyl group-containing compound (E) is more than 3,000. In the production method according to the prior art (Patent Document 1), in the case of a low molecular weight silyl group-containing compound, production with few by-products is possible, but in the case of a silyl group-containing compound with a large molecular weight, the selectivity of the silylated product decreases. For example, in Experimental Example 2-10 of a silyl group-containing organic polymer with a molecular weight of about 1,400, 8% of the isomer (1-propenyl group) as a by-product was produced, and the yield of the silylated product remained at 92%. On the other hand, in the method disclosed in the present invention, even when using a large molecular weight allyl group-containing compound (C) as a raw material to produce a silyl group-containing organic polymer with a number average molecular weight of more than 3,000, further more than 10,000, and further more than 20,000, high selectivity is shown, and it is possible to produce a silylated product with few by-products (1-propenyl group or propyl group). Therefore, the catalyst and production method of the present invention are particularly suitable for the production of a silyl group-containing organic polymer (E a ). When the silyl group-containing organic polymer (E a ) is particularly a hydrolyzable silyl group-containing organic polymer, it can be used as a curable resin such as an adhesive, a sealing material, an elastic coating agent, or an adhesive, and thus is industrially useful. The curable composition containing the hydrolyzable silyl group-containing organic polymer according to the present invention exhibits more excellent curability, and further, the rubbery cured product obtained after curing can exhibit higher modulus, tensile strength, etc.

[0030] (Polymer skeleton of the silyl group-containing organic polymer (E a )) The silyl group-containing organic polymer (E a ) according to the present embodiment has a polymer skeleton (also referred to as a main chain structure) and a polymer chain end bonded to the polymer skeleton. The polymer skeleton is a structure in which a plurality of monomers are bonded by addition, condensation, etc. to form a continuous plurality of monomer units. The monomer species contained in the polymer skeleton may be one type, or a plurality of types may be mixed and bonded.

[0031] The polymer chain end refers to a site located at the end of the polymer skeleton. The silyl group-containing organic polymer (E a) The number of polymer chain ends is 2 when all of the polymer skeletons are linear, and is 3 or more when all of the polymer skeletons are branched-chain. Also, when the polymer skeleton is a mixture of linear and branched-chain, it can also have an average value between 2 and 3.

[0032] The silyl group-containing organic polymer (E a ) may be present in the polymer skeleton and / or in the polymer chain ends. Also, two or more silyl groups may be present in one polymer chain end. The silyl group-containing organic polymer (E a ) can be used as a curable resin such as an adhesive, a sealing material, an elastic coating agent, or an adhesive when the silyl group it has is a hydrolyzable silyl group. The hydrolyzable silyl group is preferably contained in the polymer chain ends of the silyl group-containing organic polymer (E a ). Hereinafter, when explaining the curable resin, the curable composition, and the cured product, these will be explanations when the silyl group of the silyl group-containing organic polymer (E a ) is a hydrolyzable silyl group.

[0033] The silyl group-containing organic polymer (E a) The polymer backbone (also referred to as the main chain structure) is not particularly limited, and various main chain structures can be used. Specifically, polyoxyalkylene polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer; hydrocarbon polymers such as ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, etc., and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; polyester polymers obtained by condensation of dibasic acids such as adipic acid and glycols, or ring-opening polymerization of lactones; (meth)acrylic acid ester polymers obtained by radical polymerization of (meth)acrylic acid ester monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate; vinyl copolymers obtained by radical polymerization of monomers such as (meth)acrylic acid ester monomers, vinyl acetate, acrylonitrile, styrene; polysulfide polymers; polyamide polymers; polycarbonate polymers, diallyl phthalate polymers, etc. In the above description, (meth)acrylic represents acrylic and / or methacrylic.

[0034] Among these, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth)acrylic acid ester polymers are preferred because they have a relatively low glass transition temperature and the resulting cured products have excellent cold resistance. Only one of these may be used, or two or more may be used in combination.

[0035] Silyl group-containing organic polymer (E a) is a hydrolyzable silyl group-containing organic polymer, a polyoxyalkylene polymer and a (meth)acrylate polymer are particularly preferable because they have high moisture permeability and are excellent in deep part curability and adhesiveness when made into a one-component curable composition. A polyoxyalkylene polymer is more preferable, and polyoxypropylene is even more preferable.

[0036] The polyoxyalkylene polymer is preferably a polymer having a repeating unit represented by -R-O- (wherein R is a linear or branched alkylene group having 1 to 14 carbon atoms). More preferably, R is a linear or branched alkylene group having 2 to 4 carbon atoms. Specific examples of the repeating unit represented by -R-O- include -CH 2 O-, -CH 2 CH 2 O-, -CH 2 CH(CH 3 )O-, -CH 2 CH(C 2 H 5 )O-, -CH 2 C(CH 3 )(CH 3 )O-, -CH 2 CH 2 CH 2 CH 2 O- and the like. The main chain structure of the polyoxyalkylene polymer may be composed of only one type of repeating unit or may be composed of two or more types of repeating units.

[0037] In particular, when the silyl group-containing organic polymer (E a ) according to the present embodiment is a hydrolyzable silyl group-containing organic polymer and is used as a curable resin such as a sealant or an adhesive, a polyoxypropylene polymer having an oxypropylene repeating unit of 50% by weight or more, more preferably 80% by weight or more of the polymer skeleton, is preferable because it is amorphous and has a relatively low viscosity.

[0038] The main chain structure of the polyoxyalkylene polymer may be linear or may have branched chains. When it has branched chains, the number of branched chains is preferably 1 to 6 (i.e., the number of terminal groups is 3 to 8), more preferably 1 to 4 (i.e., the number of terminal groups is 3 to 6), and most preferably 1 (i.e., the number of terminal groups is 3). By having branched chains, the effect of improving the restorability of the cured product can be obtained. Also, the effect of reducing the water absorption of the cured product can be expected.

[0039] The polyoxyalkylene polymer is preferably obtained by ring-opening polymerization reaction of a cyclic ether compound using a polymerization catalyst in the presence of an initiator.

[0040] Examples of the cyclic ether compound include ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, tetrahydrofuran, etc. These cyclic ether compounds may be used alone or in combination of two or more. Among these cyclic ether compounds, since an amorphous and relatively low-viscosity polyether polymer can be obtained, it is particularly preferable to use propylene oxide.

[0041] Specific examples of the initiator include alcohols such as butanol, ethylene glycol, propylene glycol, propylene glycol monoalkyl ether, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol, sorbitol; hydroxyl-terminated polyoxyalkylene polymers having a number average molecular weight of 300 to 4,000, such as polyoxypropylene diol, polyoxypropylene triol, polyoxyethylene diol, polyoxyethylene triol, etc.

[0042] As a method for synthesizing a polyoxyalkylene polymer, for example, a polymerization method using an alkali catalyst such as KOH, a polymerization method using a transition metal compound-porphyrin complex catalyst such as a complex obtained by reacting an organoaluminum compound and porphyrin shown in JP-A-61-215623, JP-B-46-27250, JP-B-59-15336, US Patent No. 3278457, US Patent No. 3278458, US Patent No. 3278459, US Patent No. 3427256, US Patent No. 3427334, US Patent No. 3427335, etc., a polymerization method using a catalyst composed of a polyphosphazene salt exemplified in JP-A-10-273512, a polymerization method using a catalyst composed of a phosphazene compound exemplified in JP-A-11-060722, etc. can be mentioned, and it is not particularly limited. For reasons such as production cost and obtaining a polymer with a narrow molecular weight distribution, the polymerization method using a double metal cyanide complex catalyst is more preferable.

[0043] The silyl group-containing organic polymer (E a ) may be a polyoxyalkylene polymer containing other bonds such as urethane bonds and urea bonds in the polymer skeleton.

[0044] The silyl group-containing organic polymer (E a ) is not particularly limited in terms of molecular weight distribution (Mw / Mn), but is preferably 1.6 or less, more preferably 1.4 or less, still more preferably 1.3 or less, and particularly preferably 1.2 or less. When within the above range, it becomes a polymer that is relatively low in viscosity and easy to handle. The molecular weight distribution of the silyl group-containing organic polymer (E a ) can be determined from the number average molecular weight and the weight average molecular weight obtained by GPC measurement.

[0045] The silyl group-containing organic polymer (E a) The number average molecular weight is more than 3,000, preferably more than 10,000, and more preferably more than 20,000, as the polystyrene equivalent molecular weight in GPC. When the number average molecular weight is large, the cured product shows high elongation and excellent mechanical properties. It is preferably in the range of 8,000 to 100,000, more preferably 8,000 to 50,000, and particularly preferably 8,000 to 35,000. When the number average molecular weight is within these ranges, a silyl group-containing organic polymer (E a ) with excellent mechanical properties of the cured product, good curability, and easy handling viscosity and excellent workability can be obtained.

[0046] The molecular weight of the silyl group-containing organic polymer (E a ) can also be shown by the end-group molecular weight obtained by directly measuring the end-group concentration by titration analysis based on the measurement method of the hydroxyl value in JIS K 1557-1 and the principle of the measurement method of the iodine value specified in JIS K 0070 for the polymer precursor before silyl group introduction, considering the structure of the organic polymer (the degree of branching determined by the polymerization initiator used). The end-group equivalent molecular weight of the silyl group-containing organic polymer (E a ) can also be obtained by creating a calibration curve of the number average molecular weight obtained by general GPC measurement of the polymer precursor and the above end-group equivalent molecular weight, and converting the number average molecular weight obtained by GPC of the silyl group-containing organic polymer (E a ) into the end-group equivalent molecular weight.

[0047] The pH of the silyl group-containing organic polymer (E a ) is not particularly limited, but is preferably 5.0 to 9.0, more preferably 6.0 to 8.0, and even more preferably 6.5 to 7.5. When the pH of the silyl group-containing organic polymer (E a ) is within the above range, when the silyl group-containing organic polymer (E a ) is a hydrolyzable silyl group-containing organic polymer, the acidic component and the basic component that promote the hydrolysis reaction of the silyl group are less, and a silyl group-containing organic polymer (E a ) with excellent storage stability is easily obtained.

[0048] Organic polymer (E) containing a silyl group a When obtaining a hydrolyzable silyl group-containing organic polymer suitable for adhesives, sealants, etc., from the viewpoint of curability and physical properties after curing, as the hydrosilane compound (D), trimethoxysilane and dimethoxymethylsilane are particularly preferred.

[0049] <Manufacturing method> (Method for producing ruthenium nanoparticle catalyst (A) and its precursor nanoparticle (A')) The method for producing the ruthenium nanoparticle catalyst (A) and its precursor (A') is not particularly limited, and it can be produced by a method according to a known production method. For example, a production method according to the method described in JP 2021-123545 etc. can be adopted. A, A', A'', B, B', and the organic solvent used in the steps described below are as described in the above paragraph. <Step 1> Step of preparing a ruthenium nanoparticle catalyst precursor (A') from a ruthenium compound (A'') The ruthenium compound (A'') is heated in an organic solvent at 50 to 250 °C to produce a ruthenium nanoparticle catalyst precursor (A'). The specific production conditions in <Step 1> are as follows. The heating temperature in the method for preparing the ruthenium nanoparticle catalyst precursor (A') is 50 °C or higher and 250 °C or lower, and it is preferably below the boiling point of the organic solvent. It is particularly preferred to heat to the boiling point of the organic solvent and perform heating under reflux. As the organic solvent, a coordinating organic solvent is preferred, and examples of preferred coordinating organic solvents are as described above. The aging time in the method for preparing the ruthenium nanoparticle catalyst precursor (A') is not particularly limited as long as the catalytic function can be obtained, but it is usually 1 hour or longer, and preferably 24 hours or shorter. The preparation of the ruthenium nanoparticle catalyst precursor (A') is preferably carried out with stirring. For example, in stirring using a magnetic stirrer or a stir bar, the rotation speed is usually preferably 500 rpm or higher and 2,000 rpm or lower, but it is not particularly limited. When preparing the ruthenium nanoparticle catalyst precursor (A'), if the ruthenium element concentration in the dispersion is high, the ruthenium particles may not be small enough and nanoparticles may not be obtained. Therefore, the ruthenium element concentration is preferably less than 100 mM (mmol / L), and more preferably 10 mM (mmol / L) or less.

[0050] Examples of the raw material (A'') for the ruthenium nanoparticle catalyst (A) and its precursor (A') include anhydrides and hydrates of compounds selected from ruthenium(III) chloride, ruthenium(III) bromide, and ruthenium(III) iodide.

[0051] <Step 2> Step of preparing the ruthenium nanoparticle catalyst (A) from the ruthenium nanoparticle catalyst precursor (A') The ruthenium nanoparticle catalyst (A) is produced by coordinating a ligand (B) to the ruthenium nanoparticle catalyst precursor (A'). Examples of the method for producing the ruthenium nanoparticle catalyst (A) include a method of dispersing the ruthenium nanoparticle catalyst precursor (A') in an organic solvent or an allyl group-containing compound (C) and adding the ligand (B). In order to efficiently coordinate the ligand (B), it is preferable to add 1 mol equivalent or more of the ligand (B) with respect to the ruthenium element contained in the ruthenium nanoparticle catalyst precursor (A'). The preparation of the ruthenium nanoparticle catalyst (A) is preferably carried out with stirring. For example, in stirring using a magnetic stirrer or a stir bar, the rotation speed is usually preferably 500 rpm or more and 2,000 rpm or less, but is not particularly limited.

[0052] <Step 3> In the method for producing the silyl group-containing compound (E) according to an embodiment of the present invention, after producing the ruthenium nanoparticle catalyst (A) by Steps 1 and 2, an allyl group-containing compound (C) and a hydrosilane compound (D) are subjected to a hydrosilylation reaction in the presence of the ruthenium nanoparticle catalyst (A) as a hydrosilylation reaction catalyst. The ruthenium nanoparticle catalyst (A), the allyl group-containing compound (C), the hydrosilane compound (D), and the silyl group-containing compound (E) are as described above. Hereinafter, the reaction conditions of Step 3 will be described in detail.

[0053] <Reaction conditions> The amount (charged amount) of the hydrosilane compound (D) used in the reaction step is preferably 1 molar equivalent or more, more preferably 3 molar equivalents or more, and even more preferably 5 molar equivalents or more in terms of the amount of substance with respect to the allyl group contained in the allyl group-containing compound (C). Usually, it is 20 molar equivalents or less, preferably 10 molar equivalents or less. Within the above range, the silyl group can be introduced with high efficiency while suppressing the production cost. Also, within the above range, the viscosity of the silyl group-containing organic polymer (E a ) can be kept low, and a polymer with good workability can be obtained.

[0054] The amount (charged amount) of the ruthenium nanoparticle catalyst (A) used in the reaction step, with respect to the allyl group-containing compound (C), the lower limit of the weight ratio of the ruthenium element derived from the ruthenium nanoparticle catalyst (A) used is, for example, 0.01 ppm or more, 0.1 ppm or more. On the other hand, with respect to the allyl group-containing compound (C), the weight ratio of the ruthenium element derived from the ruthenium nanoparticle catalyst (A) used is preferably 0.1% or less, more preferably 100 ppm or less, and even more preferably 10 ppm or less. Within the above range, the silyl group can be introduced with high efficiency while suppressing the production cost and coloring.

[0055] The reaction process may use a solvent or may be solvent-free. When using a solvent, the type of solvent is not particularly limited, and examples include hydrocarbon solvents such as hexane and halogen solvents such as dichloromethane, which are compounds that do not react with the raw materials and catalysts. The solvent is preferably used after dehydration and deoxygenation.

[0056] The reaction temperature of the reaction process can be appropriately determined in view of reactivity (reaction rate) and the heat resistance temperature of the reaction vessel, etc. Usually, it is 0 °C or higher, preferably 20 °C or higher, more preferably 40 °C or higher, and usually 200 °C or lower, preferably 150 °C or lower. The higher the reaction temperature, the shorter the reaction time may be completed, and side reactions may be suppressed in some cases. The reaction time is not particularly limited either and may be about 5 minutes to 12 hours, or may be about 10 minutes to 5 hours.

[0057] The reaction process is preferably carried out under an inert atmosphere such as nitrogen or argon.

[0058] Also, during this reaction, in addition to the ruthenium nanoparticle catalyst (A) in the reaction system, adding and mixing a ligand (B) is preferable because the silylation rate can be improved. As a factor for improving the silylation rate, for example, when the ruthenium nanoparticle catalyst (A) has a ligand (B') together with the ligand (B), the ligand (B') coordinated to the ruthenium nanoparticle catalyst (A) exchanges with the free ligand (B), and it is considered that the proportion of the ligand (B) among all the ligands of the ruthenium nanoparticle catalyst (A) increases. Therefore, before the start of the hydrosilylation reaction, it is preferable that the ruthenium nanoparticle catalyst (A) and the ligand (B) come into contact. For example, while stirring the allyl group-containing compound (C) charged into the reaction tank at a predetermined temperature, adding and mixing the ruthenium nanoparticle catalyst (A) and the ligand (B), and then adding the hydrosilane compound (D) is an example of a preferred embodiment. The time interval from adding the ruthenium nanoparticle catalyst (A) and the ligand (B) to adding the hydrosilane compound (D) is not particularly limited and can be appropriately determined in view of the desired introduction rate of the silyl group and the time required for production, etc.

[0059] <Engineering 3'> In the method for producing the silyl group-containing compound (E) according to an embodiment of the present invention, a method using a ruthenium nanoparticle catalyst precursor (A') and not using a previously synthesized ruthenium nanoparticle catalyst (A) is also included. Specifically, it is a step of mixing the ruthenium nanoparticle catalyst precursor (A') produced in the above <Step 1>, the ligand (B), the allyl group-containing compound (C), and the hydrosilane compound (D) and subjecting them to a hydrosilylation reaction. According to this production method, a silylated product can be efficiently produced. The allyl group-containing compound (C), the hydrosilane compound (D), and the ligand (B) are as described above. The mixing order of the allyl group-containing compound (C), the hydrosilane compound (D), the ruthenium nanoparticle catalyst precursor (A'), and the ligand (B) is not particularly defined, and they can be mixed in any order. Hereinafter, the "reaction conditions" will be described in detail.

[0060] <Reaction Conditions> The preferred amount (charged amount) of the hydrosilane compound (D) used in the reaction step, the type of solvent used in the reaction step, and the preferred conditions for the reaction temperature are the same as the conditions shown in the embodiment of the step of "subjecting the allyl group-containing compound (C) and the hydrosilane compound (D) to a hydrosilylation reaction in the presence of the ruthenium nanoparticle catalyst (A)". The preferred amount (charged amount) of the ruthenium nanoparticle catalyst precursor (A') used is the same as the amount (charged amount) of the ruthenium nanoparticle catalyst (A) described above. In this production method, an operation of mixing the ruthenium nanoparticle catalyst precursor (A') and the ligand (B) in a reaction vessel to generate the ruthenium nanoparticle catalyst (A) in the system is included. Therefore, for example, while stirring the allyl group-containing compound (C) charged in the reaction vessel at a predetermined temperature, the ruthenium nanoparticle catalyst precursor (A') and the ligand (B) are added, and then the hydrosilane compound (D) is preferably added. The time interval from the addition of the ruthenium nanoparticle catalyst precursor (A') and the ligand (B) to the addition of the hydrosilane compound (D) is not particularly limited, and can be appropriately determined in view of the introduction rate of the target silyl group and the production time.

[0061] The addition amount of the ligand (B) is not particularly limited, and with respect to the allyl group-containing compound (C), it is usually 0.01 ppm or more, preferably 0.1 ppm or more, more preferably 1 ppm or more, and usually 10% or less, preferably 1% or less, more preferably 0.1% or less, by weight ratio.

[0062] According to the method for producing the silyl group-containing compound (E) described above, a mixture containing the silyl group-containing compound (E) and the ruthenium nanoparticle catalyst (A) is obtained. In particular, as the silyl group-containing organic polymer (E a ), a polymer mixture containing a hydrolyzable silyl group-containing polymer and the ruthenium nanoparticle catalyst (A) can form a curable composition by mixing a curing catalyst into the mixture.

[0063] In the said polymer mixture, the content of the ruthenium nanoparticle catalyst (A) conforms to the usage amount (charged amount) of the ruthenium nanoparticle catalyst (A) or the ruthenium nanoparticle catalyst precursor (A') described above. Specifically, the content of the ruthenium nanoparticle catalyst (A), as ruthenium element derived from the ruthenium nanoparticle catalyst (A), is usually 0.01 ppm or more, preferably 0.1 ppm or more, more preferably 1 ppm or more, and usually 1000 ppm or less, preferably 100 ppm or less, more preferably 10 ppm or less, by weight ratio with respect to the hydrolyzable silyl group-containing polymer.

[0064] <Curable Composition> When the silyl group-containing organic polymer (E a ) is a hydrolyzable silyl group-containing organic polymer, a curable composition containing the same can be formed. Further, a cured product obtained by curing the said curable composition can be obtained. As the polymer skeleton of the silyl group-containing organic polymer (E a ), as described above, a polyoxyalkylene-based polymer is more preferable, and polyoxypropylene is even more preferable.

[0065] The curable composition containing the hydrolyzable silyl group-containing organic polymer obtained by the production method described above exhibits good curability with a short skinning time as compared with the hydrolyzable silyl group-containing organic polymer produced using a conventionally known hydrosilylation reaction catalyst such as a Karstedt catalyst. Further, the cured product obtained by curing the curable composition exhibits a high modulus. Further, it exhibits high strength.

[0066] (Curing catalyst) The curable composition according to the present embodiment preferably contains a curing catalyst for the purpose of promoting the reaction of hydrolyzing and condensing the hydrolyzable silyl group, that is, the curing reaction.

[0067] As the curing catalyst, conventionally known ones can be used. Specifically, organotin compounds, metal carboxylates, amine compounds, carboxylic acids, alkoxy metals, inorganic acids, mixtures thereof, etc. can be used.

[0068] Specific examples of the organotin compound include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), the reaction product of dibutyltin oxide and a silicate compound, the reaction product of dibutyltin oxide and a phthalic acid ester, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate), dioctyltin distearate, dioctyltin oxide, the reaction product of dioctyltin oxide and a silicate compound, etc. Due to the increasing environmental concerns in recent years, dioctyltin compounds are preferred.

[0069] Specific examples of the metal carboxylate include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, calcium carboxylate, etc. As the carboxylic acid group, the following carboxylic acids can be combined with various metals.

[0070] Specific examples of the amine compound include amines such as octylamine, 2-ethylhexylamine, laurylamine, stearylamine, piperidine, 4-methylpiperidine, hexamethyleneimine; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1,5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, diphenylguanidine; biguanides such as butylbiguanide, 1-o-tolylbiguanide, 1-phenylbiguanide; ketimine compounds, and the like.

[0071] Specific examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, versatic acid, and the like.

[0072] Specific examples of the metal alkoxide include titanium compounds such as tetrabutyl titanate, titanium tetrakis(acetylacetonate), titanium ethylacetoacetate, diisopropoxytitanium bis(ethylacetoacetate); aluminum compounds such as aluminum tris(acetylacetonate), diisopropoxyaluminum ethylacetoacetate; zirconium compounds such as zirconium tetrakis(acetylacetonate).

[0073] As other curing catalysts, fluoride anion-containing compounds, photoacid generators, and photobase generators can also be used.

[0074] Two or more different types of catalysts may be used in combination as the curing catalyst. For example, by using the above-mentioned amine compound and carboxylic acid, or amine compound and metal alkoxide in combination, there may be an effect of improving the reactivity.

[0075] As the blending amount of the curing catalyst, for example, the silyl group-containing organic polymer according to the present embodiment (E a)For 100 parts by weight, 0.001 to 20 parts by weight, 0.01 to 15 parts by weight, and 0.01 to 10 parts by weight can be mentioned. Further, among the curing catalysts, after the curable composition has cured, it may ooze out onto the surface of the cured product or contaminate the surface of the cured product. In such a case, by setting the amount of the curing catalyst used to 0.01 to 3.0 parts by weight, the surface state of the cured product can be kept good while ensuring curability.

[0076] In the curable composition according to the present embodiment, as other additives, a silicon compound, an adhesion-imparting agent, a plasticizer, a solvent, a diluent, a silicate, a filler, an anti-sagging agent, an antioxidant, a light stabilizer, an ultraviolet absorber, a physical property modifier, a tackifier resin, a compound containing an epoxy group, a photocurable substance, an oxygen-curable substance, a surface property improver, an epoxy resin, other resins, a flame retardant, and a foaming agent may be added. Further, in the curable composition according to the present embodiment, various additives may be added as necessary for the purpose of adjusting various physical properties of the composition or the cured product. Examples of such additives include, for example, a curability modifier, a radical inhibitor, a metal deactivator, an ozone deterioration inhibitor, a phosphorus-based peroxide decomposer, a lubricant, a pigment, a fungicide, and the like.

[0077] (Filler) Various fillers can be blended in the curable composition according to the present embodiment. Examples of the filler include heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, carbon black, ferric oxide, aluminum fine powder, zinc oxide, activated zinc white, PVC powder, PMMA powder, glass fiber, and filament.

[0078] The amount of the filler used is preferably 1 to 300 parts by weight, more preferably 10 to 250 parts by weight, based on 100 parts by weight of the silyl group-containing organic polymer (E a )

[0079] For the purpose of reducing the weight (lowering the specific gravity) of the composition, organic balloons or inorganic balloons may be added. A balloon is a spherical filler with a hollow interior. Examples of materials for such balloons include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran.

[0080] The amount of balloons used is preferably 0.1 to 100 parts by weight, more preferably 1 to 20 parts by weight, per 100 parts by weight of the silyl group-containing organic polymer (E a ).

[0081] (Adhesion promoter) An adhesion promoter can be added to the curable composition according to this embodiment. As the adhesion promoter, a silane coupling agent or a reaction product of a silane coupling agent can be added.

[0082] Specific examples of the silane coupling agent include amino group-containing silanes such as γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane; isocyanate group-containing silanes such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, α-isocyanatomethyltrimethoxysilane, and α-isocyanatomethyldimethoxymethylsilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldimethoxysilane; epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Further, condensates of amino group-containing silanes, condensates of amino group-containing silanes and other alkoxysilanes, etc., condensates of various silane coupling agents; reactants of amino group-containing silanes and epoxy group-containing silanes, reactants of amino group-containing silanes and (meth)acrylic group-containing silanes, etc., reactants of various silane coupling agents can also be used. The above adhesion-imparting agent may be used alone or in combination of two or more kinds.

[0083] The amount of the silane coupling agent used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the silyl group-containing organic polymer (E a ) of the present embodiment.

[0084] (Plasticizer) A plasticizer can be added to the curable composition according to this embodiment. Specific examples of the plasticizer include phthalic acid ester compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), butyl benzyl phthalate; terephthalic acid ester compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate; non-phthalic acid ester compounds such as diisononyl 1,2-cyclohexanedicarboxylate; aliphatic polycarboxylic acid ester compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, tributyl acetyl citrate; unsaturated fatty acid ester compounds such as butyl oleate, methyl acetyl ricinoleate; phenyl alkyl sulfonate; phosphate ester compounds; trimellitic acid ester compounds; chlorinated paraffin; hydrocarbon oils such as alkyl diphenyl, partially hydrogenated terphenyl; process oil; epoxy plasticizers such as epoxidized soybean oil, benzyl epoxy stearate, and the like.

[0085] In addition, a high molecular weight plasticizer can be used. Specific examples of the high molecular weight plasticizer include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more, and polyethers such as derivatives obtained by converting the hydroxy groups of these polyether polyols into ester groups, ether groups, etc.; polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, and the like. The plasticizer may be used alone or in combination of two or more.

[0086] In addition, the polymer plasticizer may not have a reactive silyl group, but may have a reactive silyl group. When having a reactive silyl group, it acts as a reactive plasticizer and can prevent the migration of the plasticizer from the cured product. When having a reactive silyl group, it is preferably 1 or less, more preferably 0.8 or less on average per molecule. When using a plasticizer having a reactive silyl group, particularly an oxyalkylene polymer having a reactive silyl group, its number average molecular weight is preferably lower than that of the silyl group-containing organic polymer (E a ).

[0087] The amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and even more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the silyl group-containing organic polymer (E a ) according to this embodiment.

[0088] (Solvent, diluent) A solvent or a diluent can be added to the curable composition according to this embodiment. The solvent and the diluent are not particularly limited, but aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers, etc. can be used. When using a solvent or a diluent, due to the problem of air pollution when the composition is used indoors, the boiling point of the solvent is preferably 150°C or higher, more preferably 200°C or higher, and particularly preferably 250°C or higher. The above solvent or diluent may be used alone or in combination of two or more.

[0089] (Anti-sagging agent) An anti-sagging agent may be added to the curable composition according to this embodiment, if necessary, to prevent sagging and improve workability. The anti-sagging agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sagging agents may be used alone or in combination of two or more.

[0090] The amount of the anti-sagging agent used is the silyl group-containing organic polymer (E a)Preferably, it is 0.1 to 20 parts by weight with respect to 100 parts by weight.

[0091] (Antioxidant) An antioxidant (anti-aging agent) can be used in the curable composition according to this embodiment. Using an antioxidant can enhance the weather resistance of the cured product. Examples of the antioxidant include hindered phenol-based, monophenol-based, bisphenol-based, and polyphenol-based ones. For example, Irganox 245, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 1330, Irganox 1520 (all of the above are manufactured by BASF); SONGNOX 1076 (manufactured by SONGWON), BHT. Similarly, Tinuvin 622LD, Tinuvin 144, Tinuvin 292, CHIMASSORB 944LD, CHIMASSORB 119FL (all of the above are manufactured by BASF); Adeka Stab LA-57, Adeka Stab LA-62, Adeka Stab LA-67, Adeka Stab LA-63, Adeka Stab LA-68 (all of the above are manufactured by ADEKA CORPORATION); Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all of the above are manufactured by Sankyo Lifetech Co., Ltd.); the hindered amine light stabilizers shown in No Crack CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) can also be used. In addition, antioxidants such as SONGNOX 4120, Naugard 445, and OKABEST CLX050 can also be used. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731.

[0092] The amount of the antioxidant used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, with respect to 100 parts by weight of the silyl group-containing organic polymer (E a )100 parts by weight.

[0093] (Light stabilizer) In the curable composition according to this embodiment, a light stabilizer can be used. When a light stabilizer is used, photo-oxidative degradation of the cured product can be prevented. Examples of the light stabilizer include benzotriazole-based, hindered amine-based, benzoate-based compounds, etc., and the hindered amine-based is particularly preferable.

[0094] The amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the silyl group-containing organic polymer (E a ) in this embodiment.

[0095] (Ultraviolet absorber) In the curable composition according to this embodiment, an ultraviolet absorber can be used. When an ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based, and metal chelate-based compounds, etc., and the benzotriazole-based is particularly preferable, and commercially available names such as Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571, Tinuvin 1600, Tinuvin B75 (all of the above are manufactured by BASF) can be mentioned.

[0096] The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the silyl group-containing organic polymer (E a ) in this embodiment.

[0097] (Physical property modifier) In the curable composition according to this embodiment, a physical property modifier for adjusting the tensile properties of the cured product generated as needed may be added. The physical property modifier is not particularly limited. For example, alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane, phenyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane; trialkylsilyl borates such as tris(trimethylsilyl) borate, tris(triethylsilyl) borate; silicone varnishes; polysiloxanes and the like can be mentioned. By using the physical property modifier, the hardness when the curable composition according to this embodiment is cured can be increased, or conversely, the hardness can be decreased and the elongation at break can be increased. The above physical property modifier may be used alone or in combination of two or more kinds.

[0098] In particular, a compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis has an effect of reducing the modulus of the cured product without deteriorating the stickiness of the surface of the cured product. A compound that generates trimethylsilanol is particularly preferable. Examples of the compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis include derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, sorbitol, etc., which are silicon compounds that generate silane monool by hydrolysis. Specifically, phenoxytrimethylsilane, tris((trimethylsiloxy)methyl)propane, etc. can be mentioned.

[0099] The amount of the physical property modifier used is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the silyl group-containing organic polymer (E a ) according to this embodiment.

[0100] (Adhesion-imparting resin) In the curable composition according to this embodiment, an adhesion - imparting resin can be added for the purpose of enhancing the adhesiveness and close adhesiveness to a substrate, or as otherwise required. There are no particular restrictions on the adhesion - imparting resin, and those commonly used can be used.

[0101] Specific examples include terpene resins, aromatic - modified terpene resins, hydrogenated terpene resins, terpene - phenol resins, phenol resins, modified phenol resins, xylene - phenol resins, cyclopentadiene - phenol resins, coumarone - indene resins, rosin - based resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low - molecular - weight polystyrene - based resins, styrene copolymer resins, styrene - based block copolymers and their hydrogenated products, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5 - C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, etc. These can be used alone or in combination of two or more.

[0102] The amount of the adhesion - imparting resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, and even more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the silyl - group - containing organic polymer (E a ).

[0103] (Compound containing an epoxy group) In the curable composition according to this embodiment, a compound containing an epoxy group can be used. When a compound having an epoxy group is used, the restorability of the cured product can be enhanced. Examples of the compound having an epoxy group include epoxidized unsaturated oils and fats, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis(2 - ethylhexyl) - 4,5 - epoxycyclohexane - 1,2 - dicarboxylate (E - PS), epoxy octyl stearate, epoxy butyl stearate, etc. can be mentioned. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight with respect to 100 parts by weight of the silyl - group - containing organic polymer (E a ).

[0104] (Photocurable substance) A photocurable substance can be used in the curable composition according to this embodiment. When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved. Many such compounds are known, including organic monomers, oligomers, resins, or compositions containing them. Representative examples include monomers, oligomers, or mixtures thereof having one to several acrylic or methacrylic unsaturated groups, unsaturated acrylic compounds, vinyl polycinnamates, or azide resins.

[0105] The amount of the photocurable substance used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the silyl group-containing organic polymer (E a )

[0106] (Oxygen-curable substance) An oxygen-curable substance can be used in the curable composition according to this embodiment. Examples of oxygen-curable substances include unsaturated compounds that can react with oxygen in the air, which react with oxygen in the air to form a cured film near the surface of the cured product and prevent stickiness on the surface and adhesion of dust and dirt to the surface of the cured product. Specific examples of oxygen-curable substances include drying oils typified by tung oil and linseed oil, and various alkyd resins obtained by modifying the compounds; acrylic polymers, epoxy resins, and silicone resins modified with drying oils; liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, and polymers of C5-C8 dienes obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene. These may be used alone or in combination of two or more.

[0107] The amount of the oxygen-curable substance used is based on 100 parts by weight of the silyl group-containing organic polymer (E a) It is preferably used in the range of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight. As described in JP-A-3-160053, the oxygen-curable substance is preferably used in combination with a photocurable substance.

[0108] (Epoxy resin) An epoxy resin can be used in combination with the curable composition according to the present embodiment. The composition added with an epoxy resin is particularly preferable as an adhesive, especially an adhesive for exterior wall tiles. Examples of the epoxy resin include bisphenol A type epoxy resins and novolak type epoxy resins.

[0109] The usage ratio of the epoxy resin and the silyl group-containing organic polymer (E a ) according to the present embodiment is preferably in the range of silyl group-containing organic polymer (E a ) / epoxy resin = 100 / 1 to 1 / 100 by weight.

[0110] When adding an epoxy resin, a curing agent for curing the epoxy resin can be used in combination with the curable composition according to the present embodiment. There is no particular limitation on the epoxy resin curing agent that can be used, and generally used epoxy resin curing agents can be used.

[0111] When using a curing agent for the epoxy resin, the usage amount is preferably in the range of 0.1 to 300 parts by weight based on 100 parts by weight of the epoxy resin.

[0112] <Preparation of curable composition> The curable composition according to the present embodiment can be prepared as a one-component type in which all the compounding components are previously compounded and sealed for storage and cured by moisture in the air after construction, or as a two-component type in which a curing catalyst, a filler, a plasticizer, water and other components are separately compounded as a curing agent and the compounded material and the organic polymer composition are mixed before use. From the viewpoint of workability, the one-component type is preferable.

[0113] When the curable composition is of the one-component type, since all the compounding components are pre-compounded, it is preferable to dehydrate and dry in advance the compounding components containing moisture before use, or to dehydrate them under reduced pressure or the like during compounding and kneading. Further, in addition to the dehydration and drying method, the storage stability is further improved by adding alkoxysilane compounds such as methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane.

[0114] <Use> The curable composition according to this embodiment can be used as an adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a waterproof material, a waterproof coating material, a mold release agent, a vibration-proof material, a vibration-damping material, a sound-proof material, a foaming material, a paint, and a spray material. The cured product obtained by curing the curable composition according to this embodiment is excellent in flexibility and adhesiveness, and thus can be suitably used as a sealing material or an adhesive.

[0115] In addition, the curable composition according to the present embodiment can be used in various applications such as liquid sealants used in electrical and electronic component materials such as back surface sealants for solar cells, electrical and electronic components such as insulating coating materials for electric wires and cables, electrical insulation materials for electrical appliances and devices, acoustic insulation materials, elastic adhesives, binders, contact adhesives, spray sealants, crack repair materials, adhesives for tiling, adhesives for asphalt waterproofing materials, powder coatings, casting materials, medical rubber materials, medical adhesives, medical adhesive sheets, medical device sealants, dental impression materials, food packaging materials, sealing materials for joints of exterior materials such as sizing boards, coating materials, anti-slip coatings, cushioning materials, primers, conductive materials for electromagnetic wave shielding, heat conductive materials, hot melt materials, potting agents for electrical and electronics, films, gaskets, concrete reinforcing materials, temporary adhesives, various molding materials, and rust and waterproof sealants for wire mesh glass and the end faces (cut portions) of laminated glass, automotive parts, large vehicle parts such as trucks and buses, train vehicle parts, aircraft parts, ship parts, electrical machine parts, and various mechanical parts. Taking an automobile as an example, it can be used in a wide variety of applications such as adhesive attachment of plastic covers, trims, flanges, bumpers, window attachments, interior members, and exterior parts. Furthermore, it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, and resin moldings, either alone or with the help of a primer, and can also be used as various types of sealing compositions and adhesive compositions. In addition, the curable composition according to the present embodiment can also be used as an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiling, an adhesive for stone cladding, an adhesive for ceiling finishing, an adhesive for floor finishing, an adhesive for wall finishing, an adhesive for vehicle panels, an adhesive for assembling electrical, electronic, and precision instruments, an adhesive for bonding leather, fiber products, fabrics, paper, boards, and rubber, a reactive post-crosslinked pressure-sensitive adhesive, a sealing material for direct glazing, a sealing material for laminated glass, a sealing material for the SSG method, or a sealing material for working joints of buildings, and as a civil engineering and bridge material. Furthermore, it can also be used as an adhesive material such as an adhesive tape or an adhesive sheet.

[0116] In the following items, preferred embodiments in the present disclosure are listed, but the present invention is not limited to the following items. <1> A method for producing a ruthenium nanoparticle catalyst (A) used as a hydrosilylation catalyst when producing a silyl group-containing compound (E) having a number average molecular weight of more than 3,000 and a terminal silylation rate of 85% or more, comprising: Step 1 of heating a ruthenium compound (A'') in an organic solvent at 50 to 250 °C to produce a ruthenium nanoparticle catalyst precursor (A'); and Step 2 of coordinating a ligand (B) having a benzene ring skeleton or a norbornadiene skeleton, and having at least one halogeno group selected from the group consisting of a fluoro group, a bromo group, and an iodo group bonded to at least one of the carbon atoms in the skeleton, to the ruthenium nanoparticle catalyst precursor (A') to produce a ruthenium nanoparticle catalyst (A); A production method comprising the above. <2> The production method according to <1>, wherein in Step 1, the particle size of the ruthenium nanoparticle catalyst precursor (A') is adjusted to 0.3 to 200 nm. <3> The production method according to <1> or <2>, wherein the ligand (B) is 2,3-dibromonorbornadiene or 1,3,5-tribromobenzene. <4> The production method according to <1> to <3>, wherein the organic solvent is dimethylformamide. <5> A method for producing a silyl group-containing compound (E) having a number average molecular weight of more than 3,000 and a terminal silylation rate of 85% or more, using a ruthenium nanoparticle catalyst (A) as a hydrosilylation catalyst, comprising: Step 1 of heating a ruthenium compound (A'') in an organic solvent at 50 to 250 °C to produce a ruthenium nanoparticle catalyst precursor (A'); Step 2 of coordinating a ligand (B) having a benzene ring skeleton or a norbornadiene skeleton, and having at least one halogeno group selected from the group consisting of a fluoro group, a bromo group, and an iodo group bonded to at least one of the carbon atoms in the skeleton, to the ruthenium nanoparticle catalyst precursor (A') to produce a ruthenium nanoparticle catalyst (A); and Step 3 of mixing the ruthenium nanoparticle catalyst (A), an allyl group-containing compound (C), and a hydrosilane compound (D) and performing hydrosilylation; A production method comprising the above. <6> The production method according to <5>, wherein the amount of the ruthenium nanoparticle catalyst (A) used is 0.1 to 100 ppm in terms of the weight ratio of the ruthenium element derived from the ruthenium nanoparticle catalyst (A) with respect to the allyl group-containing compound (C). <7> A production method of a silyl group-containing compound (E) having a number average molecular weight of more than 3,000 and a terminal silylation rate of 85% or more, using a ruthenium nanoparticle catalyst (A) as a hydrosilylation catalyst, Step 1 of heating a ruthenium compound (A'') in an organic solvent at 50 to 250 °C to prepare a ruthenium nanoparticle catalyst precursor (A'); and Step 3' of mixing a ruthenium nanoparticle catalyst precursor (A'), a ligand (B) having a benzene ring skeleton or a norbornadiene skeleton, and at least one halogeno group selected from the group consisting of a fluoro group, a bromo group, and an iodo group bonded to at least one of the carbon atoms in the skeleton, an allyl group-containing compound (C), and a hydrosilane compound (D), and performing hydrosilylation; The manufacturing method including. <8> A silyl group-containing compound (E) produced by the production method of <5> or <7>, having a number average molecular weight of more than 3,000 and a terminal silylation rate of 85% or more. <9> The silyl group-containing compound (E) according to <8>, wherein the ruthenium element content derived from the ruthenium nanoparticle catalyst (A) is 0.1 to 10 ppm.

Examples

[0117] The present invention will be described in more detail with reference to the following examples. The number average molecular weight in the examples is the GPC molecular weight measured under the following conditions. Liquid delivery system: HLC-8420GPC manufactured by Tosoh Column: TSKgel SuperH series manufactured by Tosoh Solvent: THF (tetrahydrofuran) Molecular weight: Polystyrene conversion Measurement temperature: 40 °C

[0118] The ratio of the silyl group, allyl group, 1-propenyl group, or propyl group was calculated using the following nuclear magnetic resonance apparatus (NMR). 1 It was carried out by 1H NMR measurement. Apparatus: AVANCE III HD500 type digital apparatus (manufactured by BRUKER)

[0119] (Synthesis Example 1) To 41.5 mg of ruthenium chloride, 1.8 mL of pure water and 0.2 mL of 36% hydrochloric acid were added, stirred, and then allowed to stand for 6 hours to obtain a 100 mM ruthenium chloride solution. In a three-necked round-bottom flask, 50 mL of DMF (dimethylformamide) was stirred at 140 °C for 10 minutes, then 500 μL of the ruthenium chloride solution was added, and the mixture was heated under reflux at 140 °C for 9 hours to obtain a DMF dispersion of 1.0 mM (mmol / L) ruthenium nanoparticle catalyst (A-1). The solution was transparent, and no particle sedimentation was observed one week after the synthesis, so it was judged that nanoparticles were formed.

[0120] (Synthesis Example 2) To 0.415 g of ruthenium chloride, 1.8 mL of pure water and 0.2 mL of 36% hydrochloric acid were added, stirred, and then allowed to stand for 6 hours to obtain a 1.0 M ruthenium chloride solution. In a three-necked round-bottom flask, 20 mL of DMF (dimethylformamide) was stirred at 140 °C for 10 minutes, then 200 μL of the ruthenium chloride solution was added, and the mixture was heated under reflux at 140 °C for 9 hours to obtain a DMF dispersion of 10 mM (mmol / L) ruthenium nanoparticle catalyst (A-2). The solution was transparent, and no particle sedimentation was observed one week after the synthesis, so it was judged that nanoparticles were formed.

[0121] (Synthesis Example 3) Using polyoxypropylene glycol with a number average molecular weight of about 4,500 as an initiator, the polymerization of propylene oxide was carried out with a zinc hexacyanocobaltate glyme complex catalyst to obtain a hydroxyl group-containing organic polymer (F-1) with a number average molecular weight of 27,600 and hydroxyl groups at both ends. To the hydroxyl group-containing organic polymer (F-1), 1.1 molar equivalents of sodium methoxide with respect to the hydroxyl group of the polymer (F-1) was added as a 28% methanol solution. After distilling off methanol by distillation under reduced pressure, 1.3 molar equivalents of allyl chloride with respect to the hydroxyl group of the polymer (F-1) was added and the reaction was carried out at 130 °C for 1 hour. Then, allyl chloride was distilled off under reduced pressure. The obtained unpurified allyl group-containing organic polymer was mixed and stirred with n-hexane and water, and then water was removed by centrifugation. Hexane was distilled off under reduced pressure from the obtained hexane solution to remove metal salts in the polymer. Thus, a linear allyl group-containing organic polymer (C-1) which is an allyl group-containing compound (C) was obtained. The number average molecular weight of the polymer was 27,600.

[0122] (Example 1) To the polymer (C-1) obtained in Synthesis Example 3, a DMF dispersion of the ruthenium nanoparticle catalyst (A-1) obtained in Synthesis Example 1 was added so that the amount of ruthenium element became 10 ppm, and DMF was distilled off under reduced pressure while stirring at 110 °C. Subsequently, 500 ppm of 2,3-dibromonorbornadiene was added and stirred at 110 °C for 10 minutes. Further, 5.0 molar equivalents of dimethoxymethylsilane with respect to the allyl group possessed by the polymer (C-1) was added and hydrosilylation was carried out at 110 °C. 1 After confirming by 1H NMR measurement that the allyl group possessed by the polymer (C-1) was completely consumed, volatile components were distilled off under reduced pressure to obtain a polymer (E-1) which is a silyl group-containing compound (E). The obtained polymer was 1 By 1H NMR measurement, the ratio of each group with respect to the total of the silyl group, allyl group, 1-propenyl group, and propyl group was calculated. The results are shown in Table 1.

[0123] (Example 2) To the polymer (C-1) obtained in Synthesis Example 3, a DMF dispersion of the ruthenium nanoparticle catalyst (A-2) obtained in Synthesis Example 2 was added so that the amount of ruthenium element was 10 ppm, and DMF was distilled off under reduced pressure while stirring at 110 °C. Subsequently, a chloroform solution of 300 ppm of 1,3,5-tribromobenzene was added, and the mixture was stirred at 110 °C for 10 minutes while distilling off chloroform under reduced pressure. Further, 5.0 molar equivalents of dimethoxymethylsilane was added to the allyl group of the polymer (C-1), and hydrosilylation was carried out at 110 °C. 1 After confirming by 1H NMR measurement that the allyl group of the polymer (C-1) was completely consumed, volatile components were distilled off under reduced pressure to obtain a polymer (E-2) which is a silyl group-containing compound (E). The obtained polymer was 1 The ratio of each group to the total of the silyl group, allyl group, 1-propenyl group, and propyl group was calculated by 1H NMR measurement. The results are shown in Table 1.

[0124] (Example 3) To the polymer (C-1) obtained in Synthesis Example 3, a DMF dispersion of the ruthenium nanoparticle catalyst (A-2) obtained in Synthesis Example 2 was added so that the amount of ruthenium element was 5 ppm, and DMF was distilled off under reduced pressure while stirring at 110 °C. Subsequently, a chloroform solution of 150 ppm of 1,3,5-tribromobenzene was added, and the mixture was stirred at 110 °C for 10 minutes while distilling off chloroform under reduced pressure. Further, 5.0 molar equivalents of dimethoxymethylsilane was added to the allyl group of the polymer (C-1), and hydrosilylation was carried out at 110 °C. 1 After confirming by 1H NMR measurement that the allyl group of the polymer (C-1) was completely consumed, volatile components were distilled off under reduced pressure to obtain a polymer (E-3) which is a silyl group-containing compound (E). The obtained polymer was 1 The ratio of each group to the total of the silyl group, allyl group, 1-propenyl group, and propyl group was calculated by 1H NMR measurement. The results are shown in Table 1.

[0125] (Comparative Example 1) To the polymer (C-1) obtained in Synthesis Example 3, as shown in Table 1, 50 ppm of a commercially available Karstedt catalyst (platinum divinyldisiloxane complex (isopropanol solution containing 3% by weight of platinum in terms of platinum)), and 5.0 molar equivalents of dimethoxymethylsilane were added to the allyl groups of the polymer (C-1), and hydrosilylation was carried out at 110 °C. 1 After confirming by 1H NMR measurement that the allyl groups of the polymer (C-1) were completely consumed, volatile components were distilled off under reduced pressure to obtain a silyl group-containing polymer (E'-1). The obtained polymer was 1 The ratio of each group to the total of the silyl group, allyl group, 1-propenyl group, and propyl group was calculated by 1H NMR measurement. The results are shown in Table 1.

[0126] (Comparative Example 2) To the polymer (C-1) obtained in Synthesis Example 3, a DMF dispersion of the ruthenium nanoparticle catalyst (A-1) obtained in Synthesis Example 1 was added so that the amount of ruthenium element was 10 ppm, and DMF was distilled off under reduced pressure while stirring at 110 °C. Subsequently, 5.0 molar equivalents of dimethoxymethylsilane were added to the allyl groups of the polymer (C-1), and hydrosilylation was carried out at 110 °C. 1 After confirming by 1H NMR measurement that the allyl groups of the polymer (C-1) were completely consumed, volatile components were distilled off under reduced pressure to obtain a silyl group-containing polymer (E'-2). The obtained polymer was 1 The ratio of each group to the total of the silyl group, allyl group, 1-propenyl group, and propyl group was calculated by 1H NMR measurement. The results are shown in Table 1.

[0127] (Comparative Example 3) To the polymer (C-1) obtained in Synthesis Example 3, an aqueous solution of ruthenium chloride (A''-1) at 1.0 mM (mmol / L) was added (equivalent to 10 ppm of ruthenium element with respect to the polymer (C-1)), and water was distilled off under reduced pressure while stirring at 110°C. Subsequently, 500 ppm of 2,3-dibromonorbornadiene was added, and the mixture was stirred at 110°C for 10 minutes. Further, 5.0 molar equivalents of dimethoxymethylsilane was added with respect to the allyl group possessed by the polymer (C-1), and hydrosilylation was carried out at 110°C. It was confirmed by 1 1H NMR measurement that a part of the allyl group possessed by the polymer (C-1) still remained 4 hours after the start of the reaction. The volatile components were distilled off under reduced pressure 4 hours after the start of the reaction to obtain a silyl group-containing polymer (E'-3). The obtained polymer was 1 analyzed by 1H NMR measurement to calculate the ratio of each group with respect to the total of the silyl group, allyl group, 1-propenyl group, and propyl group. The results are shown in Table 1.

[0128] (Synthesis Example 4) To 0.415 g of ruthenium chloride, 1.8 mL of pure water and 0.2 mL of 36% hydrochloric acid were added and stirred, and then left standing for 6 hours to obtain a 1.0 M ruthenium chloride solution. In a three-necked round-bottom flask, 5 mL of DMF (dimethylformamide) was stirred at 140°C for 10 minutes, then 500 μL of the ruthenium chloride solution was added, and the mixture was heated to reflux at 140°C for 9 hours. A DMF dispersion of a 100 mM (mmol / L) ruthenium particle catalyst (A''-2) was obtained. Since the liquid was not transparent and sedimentation of the particles was visually confirmed one week after the synthesis, it was judged that nanoparticles were not formed.

[0129] (Comparative Example 4) To the polymer (C-1) obtained in Synthesis Example 3, a DMF dispersion of the ruthenium particle catalyst (A''-2) obtained in Synthesis Example 4 was added (equivalent to 10 ppm of ruthenium element based on the polymer (C-1)), and water was distilled off under reduced pressure while stirring at 110 °C. Subsequently, a chloroform solution of 300 ppm of 1,3,5-tribromobenzene was added, and the mixture was stirred at 110 °C for 10 minutes while distilling off chloroform under reduced pressure. Further, 5.0 molar equivalents of dimethoxymethylsilane was added to the allyl group of the polymer (C-1), and hydrosilylation was carried out at 110 °C. 1 By 1H NMR measurement, since the consumption of the allyl group of the polymer (C-1) was slow 2 hours after the start of the reaction, the reaction was stopped, and volatile components were distilled off under reduced pressure to obtain a polymer (E'-4) which is a silyl group-containing compound (E). The obtained polymer was 1 By 1H NMR measurement, the ratio of each group to the total of the silyl group, allyl group, 1-propenyl group, and propyl group was calculated. The results are shown in Table 1. It was suggested that the ruthenium catalyst that was not nanoparticulated was inferior in reactivity to the ruthenium nanoparticle catalyst at a ruthenium element amount of 10 ppm.

[0130]

Table 1

[0131] Regarding the ratio of the silyl group to the total of the silyl group, allyl group, 1-propenyl group, and propyl group, when comparing Examples 1 to 3 with Comparative Examples 1 to 5, the ratio was less than 85% in Comparative Examples 1 to 5, while it exceeded 85% in Examples 1 to 3. Side reactions were suppressed, and the silyl group could be introduced more selectively (Table 1). Furthermore, Examples 1 and 2 showed better catalytic activity with a shorter reaction completion time compared to Comparative Examples 2 to 4, which had the same ruthenium content of 10 ppm. Also, when comparing the pH of the polymers obtained in Example 1 and Comparative Example 3, the pH of the silyl group-containing polymer (E'-3) obtained in Comparative Example 3 was 5.9, while the pH of the silyl group-containing polymer (E-1) obtained in Example 1 was 6.9. It can be seen that in Example 1, a polymer with less acidic components was obtained. This is also an advantage of converting ruthenium chloride into a ruthenium nanoparticle catalyst and using it as a hydrosilylation catalyst.

[0132] (Synthesis Example 5) In a three-necked round-bottom flask, 50 mL of DMF (dimethylformamide) was stirred at 140 °C for 10 minutes, then 26 mg of hexachloroplatinic(IV) acid hexahydrate was added, and the mixture was heated under reflux at 140 °C for 8 hours. A DMF dispersion of a 1 mM (mmol / L) platinum nanoparticle catalyst was obtained. The solution was transparent, and no particle sedimentation was observed one week after synthesis, so it was determined that nanoparticles were formed.

[0133] (Comparative Example 5) To the polymer (C-1) obtained in Synthesis Example 3, a DMF dispersion of the platinum nanoparticle catalyst obtained in Synthesis Example 5 was added so that the amount of platinum element became 10 ppm, and DMF was distilled off under reduced pressure while stirring at 110 °C. Subsequently, a chloroform solution of 300 ppm of 1,3,5-tribromobenzene was added, and the mixture was stirred at 110 °C for 10 minutes while chloroform was distilled off under reduced pressure. Further, 5.0 molar equivalents of dimethoxymethylsilane was added to the allyl group of the polymer (C-1), and hydrosilylation was carried out at 110 °C. After confirming by 1H NMR measurement that the allyl group of the polymer (C-1) was completely consumed, volatile components were distilled off under reduced pressure to obtain a polymer (E'-5) which is a silyl group-containing compound. The obtained polymer was subjected to 1H NMR measurement to calculate the ratio of each group to the total of the silyl group, allyl group, 1-propenyl group, and propyl group. The results are shown in Table 1.

[0134] (Synthesis Example 6) To the polymer (C-1) obtained in Synthesis Example 3, a DMF (dimethylformamide) dispersion of ruthenium chloride (the concentration of ruthenium element in the DMF dispersion is 1.0 mmol / L. Equivalent to 10 ppm of ruthenium element with respect to the polymer (C-1)) was added, and water was distilled off under reduced pressure while stirring at 110 °C. Subsequently, 500 ppm of 2,3-dibromonorbornadiene was added, and the mixture was stirred at 110 °C for 10 minutes. Further, 5.0 molar equivalents of dimethoxymethylsilane was added to the allyl group of the polymer (C-1), and hydrosilylation was carried out at 110 °C. 1 After confirming by 1H NMR measurement that the allyl group of the polymer (C-1) was completely consumed, volatile components were distilled off under reduced pressure to obtain a silyl group-containing polymer (E'-6). The pH of the polymer (E'-6) was 5.2.

[0135] (Example 4 and Comparative Example 6) The storage stabilities of the polymers (E-1) and (E'-6) were compared by the following procedure. The polymers (E-1) and (E'-6) were each placed in a separate vial, the gas phase was sealed with nitrogen, and the vial was capped and sealed. These vials were placed in an oven at 80°C and taken out after 7 days. The viscosities of the polymers (E-1) and (E'-6) were measured before and after storage at 80°C for 7 days, and the viscosity ratio was calculated by the following formula. Viscosity ratio = "Viscosity after storage (Pa·s)" ÷ "Viscosity before storage (Pa·s)" The viscosity was measured at 23°C using a viscometer RE85U (manufactured by Toki Sangyo Co., Ltd.). The viscosity ratio of the polymer (E-1) was 100%, whereas the viscosity ratio of the polymer (E'-6) was 118%. From this result, it can be seen that in Example 1 using a ruthenium nanoparticle catalyst as a hydrosilylation reaction catalyst, a polymer which is a silyl group-containing compound (E) with good storage stability was obtained. As a factor, it is considered that the pH of the polymer (E'-6) is 5.2, whereas the polymer (E-1) shows more neutrality with a pH of 6.9. That is, it is presumed that the ruthenium nanoparticle catalyst (A-1) used in the production of the polymer (E-1) had acidic components removed in its synthesis process, contributing to good storage stability.

Claims

1. A method for producing a ruthenium nanoparticle catalyst (A) used as a hydrosilylation catalyst when producing a silyl group-containing compound (E) having a number average molecular weight of more than 3,000 and a terminal silylation rate of 85% or more, comprising: Step 1 of producing a ruthenium nanoparticle catalyst precursor (A') by heating a ruthenium compound (A'') in an organic solvent at 50 to 250 °C; and Step 2 of producing a ruthenium nanoparticle catalyst (A) by coordinating a ligand (B) having a benzene ring skeleton or a norbornadiene skeleton and having at least one halogeno group selected from the group consisting of a fluoro group, a bromo group, and an iodo group bonded to at least one of the carbon atoms in the skeleton to the ruthenium nanoparticle catalyst precursor (A'); A production method comprising the above steps.

2. The production method according to claim 1, wherein in step 1, the particle size of the ruthenium nanoparticle catalyst precursor (A') is adjusted to 0.3 to 200 nm.

3. The production method according to claim 1, wherein the ligand (B) is 2,3-dibromonorbornadiene or 1,3,5-tribromobenzene.

4. The production method according to claim 1, wherein the organic solvent is dimethylformamide.

5. A method for producing a silyl group-containing compound (E) having a number average molecular weight of more than 3,000 and a terminal silylation rate of 85% or more, using a ruthenium nanoparticle catalyst (A) as a hydrosilylation catalyst, comprising: Step 1 of producing a ruthenium nanoparticle catalyst precursor (A') by heating a ruthenium compound (A'') in an organic solvent at 50 to 250 °C; Step 2 of producing a ruthenium nanoparticle catalyst (A) by coordinating a ligand (B) having a benzene ring skeleton or a norbornadiene skeleton and having at least one halogeno group selected from the group consisting of a fluoro group, a bromo group, and an iodo group bonded to at least one of the carbon atoms in the skeleton to the ruthenium nanoparticle catalyst precursor (A'); and Step 3 of mixing the ruthenium nanoparticle catalyst (A), an allyl group-containing compound (C), and a hydrosilane compound (D) and performing hydrosilylation; A production method comprising the above steps.

6. The production method according to claim 5, wherein the amount of the ruthenium nanoparticle catalyst (A) used is 0.1 to 100 ppm in terms of the weight ratio of the ruthenium element derived from the ruthenium nanoparticle catalyst (A) with respect to the allyl group-containing compound (C).

7. A method for producing a silyl group-containing compound (E) having a number average molecular weight of more than 3,000 and a terminal silylation rate of 85% or more, using a ruthenium nanoparticle catalyst (A) as a hydrosilylation catalyst, Step 1 of heating a ruthenium compound (A'') in an organic solvent at 50 to 250 °C to prepare a ruthenium nanoparticle catalyst precursor (A'); and Step 3' of mixing the ruthenium nanoparticle catalyst precursor (A'), a ligand (B) having a benzene ring skeleton or a norbornadiene skeleton, and at least one halogeno group selected from the group consisting of a fluoro group, a bromo group, and an iodo group bonded to at least one of the carbon atoms in the skeleton, an allyl group-containing compound (C), and a hydrosilane compound (D), and performing hydrosilylation; A manufacturing method comprising:

8. A silyl group-containing compound (E) having a number average molecular weight of more than 3,000 and a terminal silylation rate of 85% or more, produced by the production method according to claim 5 or 7.

9. The silyl group-containing compound (E) according to claim 8, wherein the ruthenium element content derived from the ruthenium nanoparticle catalyst (A) is 0.1 to 10 ppm.

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