Ruthenium complex, method for producing silyl group-containing compound, silyl group-containing polymer mixture, curable composition, and cured product

Abstract

A ruthenium complex (A) having a compound (B) is used as a hydrosilylation reaction catalyst. The hydrosilylation reaction catalyst is configured by mixing the compound (B) with a ruthenium compound (A ') that does not have the compound (B) as a ligand. The compound (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 an electron-withdrawing group bonded to at least one of the carbon atoms forming the carbon-carbon double bond.

Description

Technical Field

[0001] This invention relates to a method for manufacturing ruthenium complexes, silyl-containing compounds, silyl-containing polymer mixtures, curable compositions, and cured products. Background Technology

[0002] Organic polymers containing silicon atoms, particularly those with hydroxyl or hydrolyzable groups on the silicon atoms and silyl groups that can form siloxane bonds (hereinafter referred to as "hydrolyzable silyl groups"), are known as wet-reactive polymers. They cure through hydrolysis to form a flexible, rubbery cured product, and are therefore used in a variety of industrial products such as sealants, adhesives, coatings, paints, and binders.

[0003] A commonly known method for obtaining such silyl-containing organic polymers is the hydrosilylation reaction of an allyl-containing organic polymer and a hydrosilane compound in the presence of a metal catalyst. However, a common problem exists in the hydrosilylation of allyl-containing compounds using metal catalysts: side reactions such as isomerization and hydrogenation of the 1-propenyl group (internal olefin) occur during this reaction. In the hydrosilylation reaction of allyl-containing organic polymers, when using the widely used Karstedt catalyst (platinum divinyldisilazane complex), approximately 20% of the aforementioned side reactions occur, thus limiting the introduction rate of silyl groups. As a result, there is room for improvement in the modulus, tensile strength, and other properties of the rubber-like cured product formed by curing a curable composition containing the obtained hydrolyzable silyl-containing organic polymer.

[0004] On the other hand, besides platinum catalysts such as Karstedt catalysts, ruthenium catalysts are known to exhibit good activity in hydrosilylation. Patent Document 1 reports the efficient production of corresponding silane compounds by reacting allyl ether compounds with hydrosilane compounds in the presence of specific ruthenium complexes. However, when the allyl ether compound has a high molecular weight, the side reaction rate increases, and the selectivity of the silane compound decreases, thus limiting the production of silane compounds with a molecular weight of 3000 or less.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2021-11456 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] The present invention aims to provide a ruthenium complex that can efficiently introduce silane groups into the hydrosilylation reaction of allyl compounds, regardless of the molecular weight of the allyl compounds, and to provide a method for manufacturing silane-containing compounds.

[0010] Problem Solving Methods

[0011] Through dedicated research, the inventors discovered that, in the presence of a ruthenium catalyst with a specific compound as a ligand, silanes can be efficiently produced through the hydrosilylation reaction of allyl-containing compounds, regardless of the molecular weight of the allyl-containing compound. Furthermore, when using a known ruthenium catalyst for the hydrosilylation reaction of allyl-containing compounds, by pre-adding a specific compound, silanes can also be efficiently produced regardless of the molecular weight of the allyl-containing compound, thus completing this invention.

[0012] That is, the present invention relates to a ruthenium complex (A) having compound (B) as a ligand, wherein compound (B) has at least one carbon-carbon double bond in one molecule, and wherein at least one carbon atom forming the carbon-carbon double bond is bonded with an electron-withdrawing group.

[0013] In addition, the present invention also relates to a hydrogenation silylation reaction catalyst comprising the above-mentioned ruthenium complex (A).

[0014] Furthermore, the present invention also relates to a method for manufacturing a silyl-containing compound (E), comprising a step of mixing an allyl-containing compound (C), a hydrosilane compound (D), and the aforementioned hydrosilane reaction catalyst to carry out a hydrosilane reaction.

[0015] Furthermore, the present invention also relates to a manufacturing method for a silyl-containing compound (E), the method comprising a step of mixing an allyl compound (C), a hydrosilane compound (D), a ruthenium compound (A') without compound (B) as a ligand, and compound (B) to carry out a hydrosilylation reaction, wherein compound (B) has at least one carbon-carbon double bond in one molecule, and at least one carbon atom forming the carbon-carbon double bond is bonded with an electron-withdrawing group.

[0016] In addition, the present invention also relates to a polymer mixture containing a hydrolyzable silyl group and the above-mentioned ruthenium complex (A); the polymer mixture and a curable composition containing a curing catalyst; and a cured product obtained by curing the curable composition.

[0017] The effects of the invention

[0018] According to the present invention, a ruthenium complex can be provided, which is used as a catalyst in the hydrosilylation reaction of an allyl compound with a hydrosilane compound, and can efficiently introduce silyl groups regardless of the molecular weight of the allyl compound. A hydrosilylation reaction catalyst containing the ruthenium complex can also be provided. Furthermore, according to the present invention, a method for manufacturing a silyl-containing compound can be provided, which can efficiently introduce silyl groups in the hydrosilylation reaction of an allyl compound with a hydrosilane compound. In addition, a polymer mixture containing hydrolyzable silyl groups and highly inducted with silyl groups obtained by the manufacturing method of the present invention, and a curable composition containing the same, can be provided. Furthermore, a cured product obtained by curing the above-described curable composition can be provided. Detailed Implementation

[0019] The embodiments of the present invention will now be described in detail.

[0020] One embodiment of the present invention provides a ruthenium complex (A) having a compound (B) as a ligand, wherein compound (B) has at least one carbon-carbon double bond in one molecule, and at least one carbon atom forming the carbon-carbon double bond is bonded with an electron-withdrawing group. Compared with known ruthenium catalysts, this ruthenium complex (A) exhibits high selectivity when used as a catalyst for the hydrosilylation reaction of allyl compounds and hydrosilane compounds, suppressing the by-product formation of 1-propenyl or hydride (propyl), and efficiently producing the corresponding silane even when the silane is a high molecular weight silane with a number average molecular weight exceeding 3000. The ruthenium complex (A) and compound (B) will be described in detail below.

[0021] <Ruthenium complex (A)>

[0022] One embodiment of the present invention provides a ruthenium complex (A) having compound (B) as a ligand. There is no particular limitation on the specific type of ruthenium complex (A) other than having compound (B) as a ligand. The ruthenium complex (A) may have one or more types of compound (B) as a ligand.

[0023] (Method for manufacturing ruthenium complex (A))

[0024] Ruthenium complex (A) can be manufactured using a known manufacturing method. Examples of raw materials for ruthenium complex (A) include anhydrous forms and hydrates of compounds selected from ruthenium(III) chloride, ruthenium(III) bromide, and ruthenium(III) iodide. A specific method for manufacturing ruthenium complex (A) involves adding compound (B) to an ethanolic solution of ruthenium(III) chloride hydrate and heating under reflux, followed by filtration and drying to obtain ruthenium complex (A). When using ruthenium(III) chloride hydrate as a raw material, during heating under reflux, to neutralize the generated hydrogen chloride, the heating can be carried out in the presence of an alkaline compound such as sodium carbonate or sodium bicarbonate. From the viewpoint of reaction rate, when ruthenium(III) chloride hydrate reacts with compound (B), it is preferable to use compound (B) in amounts of 1 molar equivalent or more relative to the ruthenium compound used as a raw material.

[0025] Furthermore, as a ligand, the ruthenium complex (A) can have both a compound (B) and a compound (B') that is not a compound (B). Compound (B') is a compound that can coordinate with the ruthenium complex (A) but is not a compound (B). There are no particular limitations on the compounds (B') that can serve as ligands; examples include 2,5-norbornadiene ligands, 1,5-cyclooctadiene ligands, p-cymene ligands, mesitylene ligands, benzene ligands, carbonyl ligands, isocyanate ligands, and aromatic ligands.

[0026] When the ruthenium complex (A) has both compound (B) and compound (B') as ligands, a higher proportion of compound (B) among all the ligands in the ruthenium complex (A) provides better selectivity and is therefore preferred. The proportion of compound (B) among all ligands is preferably 1 to 100% mol%, more preferably 50 to 100 mol%, further preferably 70 to 100 mol%, and even more preferably 90 to 100 mol%.

[0027] A ruthenium complex (A) with compound (B) as a ligand can be obtained by the method described later: adding compound (B) to a system in which a ruthenium compound (A') without compound (B) in the ligand is present, thereby converting the ruthenium compound (A') into a ruthenium complex (A).

[0028] <Compound (B)>

[0029] Compound (B) of one embodiment of the present invention is a compound that can coordinate with a ruthenium complex. Compound (B) has at least one carbon-carbon double bond in a molecule, and at least one carbon atom forming the carbon-carbon double bond is bonded with an electron-withdrawing group.

[0030] Examples of basic skeletons containing the aforementioned carbon-carbon double bonds in compound (B) include: for example, norbornadiene skeletons, cyclooctadiene skeletons, benzene ring skeletons, benzoquinone skeletons, etc. More specifically, examples include: 2,5-norbornadiene skeletons, 1,5-cyclooctadiene skeletons, p-cymene skeletons, mesitylene skeletons, benzene ring skeletons, benzoquinone skeletons, etc. The norbornadiene skeleton or the benzene ring skeleton is preferred.

[0031] Examples of electron-withdrawing groups include halogen groups such as fluorine, chlorine, bromine, and iodo groups, as well as cyano, aldehyde, and nitro groups. When a molecule contains multiple electron-withdrawing groups, these groups can be of different types.

[0032] Compound (B) may have one or more electron-withdrawing groups in one molecule, preferably two or more, more preferably two to four, and particularly preferably two or three.

[0033] Furthermore, halogen groups are preferred as the type of electron-withdrawing group; fluorine, bromine, or iodine groups are more preferred; bromine or iodine groups are even more preferred; and bromine groups are particularly preferred. In particular, it is preferred that compound (B) has one or more electron-withdrawing groups selected from fluorine, bromine, and iodine groups in one molecule; more preferably, it has two or more. Further, it is preferred that compound (B) has one or more electron-withdrawing groups selected from bromine and iodine groups in one molecule. In this case, in addition to bromine and / or iodine groups, a fluorine group may be further present.

[0034] Preferably, these electron-withdrawing groups are directly bonded to the carbon atoms of the carbon-carbon double bond that forms compound (B). In particular, when compound (B) has a benzene ring skeleton, it is preferable that these electron-withdrawing groups are directly bonded to the benzene ring.

[0035] Compound (B) comprises the aforementioned basic skeleton and a combination of electron-withdrawing groups. The specific types of compound (B) are not particularly limited, but examples include: 2-bromonorbornene, 2,3-dibromonorbornene, 1,4-dibromobenzene and its structural isomers, 1-bromo-4-iodobenzene and its structural isomers, 1,3,5-tribromobenzene and its structural isomers, 1,2,4,5-tetrabromobenzene and its structural isomers, hexabromobenzene, 1-bromo-3,5-difluorobenzene and its structural isomers, 1-bromo-3,5-dichlorobenzene and its structural isomers, 1-bromo-3,5-diiodobenzene and its structural isomers, 1-bromo-3-chloro-5-fluorobenzene and its structural isomers, 1,4-diiodobenzene and its structural isomers, 1,3,5-triiodobenzene and its structural isomers. Isomers, 1,2,4,5-tetraiodobenzene and its structural isomers, hexaiodobenzene, 1,3-difluoro-5-iodobenzene and its structural isomers, 1,3-dichloro-5-iodobenzene and its structural isomers, 1,3-dibromo-5-iodobenzene and its structural isomers, 1,3-dibromo-5-chlorobenzene and its structural isomers, 1-chloro-3,5-diiodobenzene and its structural isomers, 1-fluoro-3,5-dibromobenzene and its structural isomers, 1-fluoro-3,5-diiodobenzene and its structural isomers, 1-chloro-3-fluoro-5-iodobenzene and its structural isomers, 1-bromo-3-chloro-5-iodobenzene and its structural isomers, 1-bromo-3-fluoro-5-iodobenzene and its structural isomers. From the viewpoint of suppressing byproducts, compound (B) is particularly preferred to be 2,3-dibromonorbornene, 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,3,5-tribromobenzene, 1,4-diiodobenzene or hexabromobenzene, 2,3-dibromonorbornene, 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene or 1,3,5-tribromobenzene. Compound (B) may be used alone or in combination of two or more compounds.

[0036] A method for producing a silyl-containing compound (E) according to one embodiment of the present invention includes a step of carrying out a hydrosilylation reaction in the presence of a ruthenium complex (A) using an allyl-containing compound (C) and a hydrosilane compound (D) as catalysts for a hydrosilylation reaction. The ruthenium complex (A) is as described above. Hereinafter, the terms "silyl-containing compound (E)," "allyl-containing compound (C)," "hydrosilane compound (D)," and "reaction conditions" will be described in detail.

[0037] <Compounds containing silane (E)>

[0038] The silyl-containing compound (E) of this embodiment is not particularly limited in its specific structure if it is a compound in which a propylene group from an allyl-containing compound (C) is bonded to a silicon atom from a hydrosilane compound (D). The silyl-containing compound (E) has a silyl group as shown in the following general formula (1).

[0039] -SiR a X b Equation (1)

[0040] In general formula (1), R represents a monovalent hydrocarbon group with 1 to 20 carbon atoms, either substituted or unsubstituted. When general formula (1) contains multiple R groups, they may be the same or different from each other. The hydrocarbon group can be either saturated or unsaturated, and can be aliphatic, alicyclic, or aromatic. The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6. It is even more preferably 1 to 3, and particularly preferably 1 or 2. When the hydrocarbon group has a substituent, there are no particular limitations on the substituent, and examples include, for instance, halogen groups such as chloro groups, alkoxy groups such as methoxy groups, and amino groups such as N,N-diethylamino groups.

[0041] Examples of R include: unsubstituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, 2-ethylhexyl, and n-dodecyl; substituted alkyl groups such as chloromethyl, methoxymethyl, and N,N-diethylaminomethyl; unsaturated hydrocarbon groups such as vinyl, isopropenyl, and allyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl, tolyl, and 1-naphthyl; and aralkyl groups such as benzyl. Substituted or unsubstituted alkyl groups are preferred, more preferably methyl, ethyl, chloromethyl, or methoxymethyl, further preferably methyl or methoxymethyl, and particularly preferably methyl. When multiple Rs are present, they may be the same or different from each other.

[0042] In general formula (1), X represents a hydroxyl group or a hydrolyzable group. When general formula (1) contains multiple X groups, they may be the same or different from each other. There is no particular limitation on the hydrolyzable group; it can be any known hydrolyzable group, such as hydrogen atom, halogen atom, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, alkenoxy group, etc. Among these, alkoxy, acyloxy, ketoximate, and alkenoxy groups are preferred. From the viewpoint of hydrolytic stability and ease of handling, alkoxy is more preferred, methoxy, ethoxy, and particularly methoxy is preferred. When multiple X groups are present, they may be the same or different from each other.

[0043] In 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, preferably 3. When the silane is a hydrolyzable silane, b represents any one of 1, 2, and 3, and from the viewpoint of curability, 2 or 3 is preferred.

[0044] The molecular weight of the silyl-containing compound (E) is not particularly limited; it can be a low-molecular-weight compound or a polymer. In the manufacturing method based on known technology (Patent Document 1), while fewer byproducts can be achieved when using a low-molecular-weight silyl-containing compound, the selectivity of the silane decreases when using a high-molecular-weight silyl-containing compound. For example, in Experimental Examples 2-10 of a silyl-containing organic polymer with a molecular weight of about 1400, 8% of the isomer (1-propenyl) was produced as a byproduct, and the yield of the silane was only 92%. On the other hand, in the method disclosed in this invention, using a high-molecular-weight allyl-containing compound (C) as a raw material, high selectivity is exhibited even when manufacturing silyl-containing organic polymers with a number average molecular weight of 3000, further 10000, and further exceeding 20000, resulting in the production of silanes with fewer byproducts (1-propenyl or hydride). Therefore, the catalyst and manufacturing method of the present invention are particularly suitable for silyl-containing organic polymers (E) in silyl-containing compounds (E). a The manufacture of ), especially of silyl-containing organic polymers (E). a When the organic polymer contains hydrolyzable silyl groups, it can be used as a curable resin for adhesives, sealants, elastic coatings, and bonding agents, and is therefore useful in industry. Curable compositions containing the hydrolyzable silyl groups of the present invention exhibit superior curability, and the resulting rubbery cured product can exhibit higher modulus, tensile strength, etc.

[0045] (organic polymers containing silyl groups (E) a (polymer backbone)

[0046] The silyl-containing organic polymer (E) of this embodiment a A polymer backbone (also known as the main chain structure) consists of polymer chain ends bonded to the polymer backbone. The polymer backbone is a structure formed by multiple monomer units bonded together through addition, condensation, etc. The polymer backbone can contain one type of monomer or a mixture of multiple types bonded together.

[0047] The aforementioned polymer chain ends refer to the portions located at the ends of the polymer backbone. When the polymer backbone is entirely linear, organic polymers containing silyl groups (E...) aThe number of polymer chain ends is 2, and when the polymer backbone is entirely branched, it is 3 or more. Additionally, when the polymer backbone is a mixture of linear and branched chains, the average number can be between 2 and 3.

[0048] Organic polymers containing silyl groups (E a The silyl groups can be present in the polymer backbone and / or at the ends of the polymer chains. Furthermore, more than two silyl groups can be present at the end of a single polymer chain. In silyl-containing organic polymers (E... a When the silyl group is a hydrolyzable silyl group, it can be used as a curable resin such as an adhesive, sealant, elastic coating, or binder. Preferably, the hydrolyzable silyl group is contained in an organic polymer containing silyl groups (E...). a In the polymer chain ends of ), the following description of curable resins, curable compositions, and cured products refers to their silyl-containing organic polymers (E). a The case where the silane is a hydrolyzable silane will be explained.

[0049] Organic polymers containing silyl groups (E a There are no particular restrictions on the polymer backbone (also known as the main chain structure) of the polymer; a variety of main chain structures can be used. Specifically, examples include: polyoxyethylene polymers such as polyoxyethylene, polyoxypropylene, polyoxybutene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutene copolymer; hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers, including copolymers of ethylene-propylene, polyisobutylene, isobutylene, and isoprene; polyester polymers obtained by condensation of dicarboxylic acids such as adipic acid with diols, or by ring-opening polymerization of lactones; (meth)acrylate polymers obtained by free radical polymerization of (meth)acrylate monomers such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and stearate methacrylate; vinyl copolymers obtained by free radical polymerization of (meth)acrylate monomers, vinyl acetate, acrylonitrile, styrene, etc.; polysulfide polymers; polyamide polymers; polycarbonate polymers; and diallyl phthalate polymers. It should be noted that in the above description, (meth)acrylic acid refers to acrylic acid and / or methacrylic acid.

[0050] Among these, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, as well as polyoxyethylene polymers and (meth)acrylate polymers, have relatively low glass transition temperatures, resulting in curing products with excellent cold resistance, and are therefore preferred. Only one of these polymers may be used, or two or more may be used in combination.

[0051] In organic polymers containing silyl groups (E a When the polymer is an organic polymer containing hydrolyzable silyl groups, polyoxyethylene polymers and (meth)acrylate polymers have high moisture permeability, excellent deep curing properties when formulated into single-component curable compositions, and excellent adhesion, making them particularly preferred. Polyoxyethylene polymers are more preferred, and polyoxypropylene polymers are even more preferred.

[0052] Polyoxyalkylene polymers are preferably polymers having repeating units represented by -RO- (where R is a linear or branched alkylene group having 1 to 14 carbon atoms). R is more preferably a linear or branched alkylene group having 2 to 4 carbon atoms. Specific examples of repeating units represented by -RO- include: -CH2O-, -CH2CH2O-, -CH2CH(CH3)O-, -CH2CH(C2H5)O-, -CH2C(CH3)(CH3)O-, -CH2CH2CH2CH2O-, etc. The main chain structure of polyoxyalkylene polymers may be formed by only one type of repeating unit or by two or more types of repeating units.

[0053] In particular, the silyl-containing organic polymer (E) of this embodiment a The product is an organic polymer containing hydrolyzable silane. When used as a curable resin such as a sealant or adhesive, a polyoxypropylene polymer having 50% or more, more preferably 80% or more of oxypropylene repeating units in the polymer backbone is amorphous and has relatively low viscosity, and is therefore preferred.

[0054] The main chain structure of the polyoxyethylene polymer can be linear or branched. When branched, the number of branches is preferably 1 to 6 (i.e., 3 to 8 terminal groups), more preferably 1 to 4 (i.e., 3 to 6 terminal groups), and most preferably 1 (i.e., 3 terminal groups). By having branches, the resilience of the cured product can be improved. Furthermore, a reduction in the water absorption of the cured product is expected.

[0055] Polyoxyolefin polymers are preferably obtained by using a polymerization catalyst in the presence of an initiator, via a ring-opening polymerization reaction of a cyclic ether compound.

[0056] Examples of cyclic ether compounds include ethylene oxide, propylene oxide, butane oxide, tetramethylene oxide, and tetrahydrofuran. These cyclic ether compounds can be used individually or in combination of two or more. Among cyclic ether compounds, propylene oxide is particularly preferred because it yields amorphous polyether polymers with relatively low viscosity.

[0057] Specifically, examples of initiators include: butanol, ethylene glycol, propylene glycol, propylene glycol monoalkyl ethers, butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, and other alcohols; and hydroxyl-terminated polyoxyethylene polymers with a number average molecular weight of 300-4000, such as polyoxypropylene glycol, polyoxypropylene triol, polyoxyethylene glycol, and polyoxyethylene triol.

[0058] Examples of methods for synthesizing polyoxyethylene polymers include: polymerization methods based on base catalysts such as KOH; polymerization methods based on transition metal compound-porphyrin complex catalysts, such as the complex obtained by reacting organoaluminum compounds with porphyrins as shown in Japanese Patent Application Publication No. 61-215623; polymerization methods based on composite metal cyanide complex catalysts as shown in Japanese Patent Publication Nos. 46-27250, 59-15336, US Patent Nos. 3278457, 3278458, 3278459, 3427256, 3427334, and 3427335; polymerization methods using catalysts containing polyphosphazene salts as exemplified in Japanese Patent Application Publication No. 10-273512; and polymerization methods using catalysts containing phosphazene compounds as exemplified in Japanese Patent Application Publication No. 11-060722, etc., without particular limitation. Considering factors such as manufacturing cost and the ability to obtain polymers with narrow molecular weight distribution, polymerization based on complex metal cyanide catalysts is preferred.

[0059] Organic polymers containing silyl groups (E a It can be a polyoxyethylene polymer that contains other bonds such as urethane bonds and urea bonds in the polymer backbone.

[0060] Organic polymers containing silyl groups (E a The molecular weight distribution (Mw / Mn) of the polymer is not particularly limited, but is preferably 1.6 or less, more preferably 1.4 or less, further preferably 1.3 or less, and particularly preferably 1.2 or less. If it is within the above range, it becomes a polymer with relatively low viscosity and easy handling. Silicone-containing organic polymers (E... a The molecular weight distribution of ) can be determined by the number-average molecular weight and weight-average molecular weight obtained by GPC.

[0061] Organic polymers containing silyl groups (E aThe number-average molecular weight (NMR) of polystyrene in GPC is preferably greater than 3000, more preferably greater than 10000, and even more preferably greater than 20000. A high NMR results in high elongation and excellent mechanical properties in the cured product. A NMR of 8000-100000 is preferred, more preferably 8000-50000, and particularly preferably 8000-35000. Within these NMR ranges, the cured product exhibits excellent mechanical properties, and furthermore, it is possible to obtain silyl-containing organic polymers (E...) that exhibit good curability, have easily operable viscosity, and thus excellent workability. a ).

[0062] Organic polymers containing silyl groups (E a The molecular weight of ) can be expressed as the molecular weight of the terminal group determined as follows: the concentration of the terminal group in the polymer precursor before the introduction of silyl group is directly determined by titration analysis based on the hydroxyl value determination method of JIS K 1557-1 and the iodine value determination method specified in JIS K 0070, and the molecular weight of the terminal group is determined by considering the structure of the organic polymer (the degree of branching determined by the polymerization initiator used). Organic polymers containing silyl group (E a The equivalent molecular weight of the terminal groups can also be determined by the following method: A standard curve of the number-average molecular weight obtained by general GPC determination of the polymer precursor and the equivalent molecular weight of the terminal groups is then used to determine the molecular weight of the polymer precursor. This curve is then used to determine the molecular weight of the silyl-containing organic polymer (E...). a The number-average molecular weight obtained from GPC is converted to the molecular weight calculated from the terminal groups.

[0063] <Allyl-containing compound (C)>

[0064] In this embodiment, the allyl-containing compound (C) is any compound having an allyl group (CH2=CH-CH2-) and capable of forming a silyl-containing compound (E) through a hydrosilylation reaction with the hydrosilane compound (D), and is not particularly limited. The reaction with the silyl-containing organic polymer (E) a Similarly, allyl-containing compounds (C) can be allyl-containing organic polymers. This is because the polymer backbone of allyl-containing organic polymers differs from that of silyl-containing organic polymers (E). a The polymer skeletons of the two are the same, so the description is omitted.

[0065] <Hydrosilane Compounds (D)>

[0066] The hydrosilane compound (D) in this embodiment is not particularly limited, but is preferably the structure shown in formula (2).

[0067] SiR a X b H 4-a-bEquation (2)

[0068] R, X, a, and b in general formula (2) are as described in general formula (1).

[0069] Specific examples of such hydrosilane compounds (D) include: for example, trimethoxysilane, triethoxysilane, triphenoxysilane, tri(2-propenoxy)silane, triacetoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, (methoxymethyl)dimethoxysilane, (methoxymethyl)diethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, etc. Oxysilanes, (N,N-diethylaminomethyl)diethoxysilane, diphenoxymethylsilane, methylsilane, dimethylsilane, trimethylsilane, ethylsilane, diethylsilane, triethylsilane, methyldiethylsilane, dimethylethylsilane, dichlorodimethylsilane, dichloromethylsilane, phenylsilane, diphenylsilane, triphenylsilane, phenylmethylsilane, phenyldimethylsilane, diphenylmethylsilane, ethylphenylsilane, diethylphenylsilane, ethyldiphenylsilane, etc.

[0070] As an organic polymer containing silyl groups (E a In the case of obtaining an organic polymer containing hydrolyzable silanes suitable for adhesives, sealants, etc., the hydrosilane compound (D) is particularly preferred from the perspective of curing properties and post-curing physical properties.

[0071] <Reaction Conditions>

[0072] Relative to the allyl group in the allyl-containing compound (C), the amount of hydrosilane compound (D) used in the reaction step, in molar terms, is preferably 1 molar equivalent or more, preferably 3 molar equivalents or more, and more preferably 5 molar equivalents or more. Additionally, it is typically 20 molar equivalents or less, preferably 10 molar equivalents or less. Within the above range, manufacturing costs can be suppressed, and silane groups can be introduced with high efficiency. Furthermore, within the above range, the manufactured silane-containing organic polymer (E) can be... a The viscosity of the polymer is suppressed to a low level, resulting in a polymer with good workability.

[0073] The amount of ruthenium complex (A) used in the reaction step, relative to the allyl compound (C), is typically 0.01 ppm or more by weight, preferably 0.1 ppm or more, more preferably 1 ppm or more, typically 10% or less, preferably 1% or less, more preferably 0.1% or less. If it is within the above range, silane can be introduced with high efficiency.

[0074] The reaction process can use a solvent or be solvent-free. When using a solvent, the type of solvent is not particularly limited, but it is preferably a compound that does not react with the raw materials or catalyst. Specifically, examples include hydrocarbon solvents such as hexane and halogen solvents such as dichloromethane. The solvent is preferably used after dehydration and deoxidation.

[0075] The reaction temperature of the reaction process can be appropriately determined based on factors such as reactivity (reaction rate) and the heat resistance temperature of the reaction vessel. It is typically above 0°C, preferably above 20°C, more preferably above 40°C, and typically below 200°C, preferably below 150°C. Higher reaction temperatures allow the reaction to terminate in a shorter time and can sometimes suppress side reactions. The reaction time is not particularly limited and can range from approximately 5 minutes to 12 hours, or from approximately 10 minutes to 5 hours.

[0076] The reaction process is preferably carried out under an inert atmosphere such as nitrogen or argon.

[0077] Furthermore, in the hydrosilylation reaction, in addition to adding the ruthenium complex (A) to the reaction system, it is preferable to further add compound (B) and mix them, as this can increase the silanization rate. As a reason for the increased silanization rate, one could consider, for example, that the amount of compound (B) used in the synthesis of the ruthenium complex (A) is insufficient, and that in the case where the ruthenium complex (A) contains a portion of ruthenium chloride (III), the ruthenium chloride (III) reacts with the added compound (B) to transform into the ruthenium complex (A). Therefore, it is preferable to contact the ruthenium complex (A) and compound (B) before the start of the hydrosilylation reaction. One example of a preferred embodiment is the method of stirring the allyl-containing compound (C) added to the reaction vessel at a given temperature, simultaneously adding the ruthenium complex (A) and compound (B), mixing them, and then adding the hydrosilane compound (D). There is no particular limitation on the time interval between the addition of ruthenium complex (A) and compound (B) and the addition of hydrosilane compound (D), which can be appropriately determined based on factors such as the introduction rate of the target silane and the time required for manufacturing.

[0078] A method for producing a silane-containing compound (E) according to one embodiment of the present invention includes a step of performing a hydrosilylation reaction by mixing an allyl compound (C), a hydrosilane compound (D), a ruthenium compound (A') without compound (B) as a ligand, and compound (B). According to this method, as described above, even without using a pre-synthesized ruthenium complex (A), the ruthenium compound (A') and compound (B) can be mixed in a reaction vessel to generate the ruthenium complex (A) in the system. By using it as a catalyst, silanes can be produced with high efficiency. Regarding the allyl compound (C), hydrosilane compound (D), and compound (B), as described above, the mixing order of the allyl compound (C), hydrosilane compound (D), ruthenium compound (A'), and compound (B) is not particularly specified and can be mixed in any order. Hereinafter, the terms "ruthenium compound (A')" and "reaction conditions" will be described in detail.

[0079] <Ruthenium compound (A')>

[0080] In one embodiment of the present invention, the ruthenium compound (A') used is not particularly limited except that it does not have compound (B) as a ligand. Ruthenium(III) chloride hydrate and ruthenium complexes having a compound (B') that is not a ligand can be used as ruthenium compound (A'). Examples of compounds (B') include, for example, 2,5-norbornadiene ligands, 1,5-cyclooctadiene ligands, p-cymene ligands, mesitylene ligands, benzene ligands, carbonyl ligands, isocyanate ligands, aromatic ligands, etc.

[0081] From the viewpoint of suppressing byproducts, the ruthenium compound (A') is preferably a ruthenium complex having a ligand selected from 2,5-norbornene ligand, benzene ligand, and p-cymene ligand.

[0082] <Reaction Conditions>

[0083] The preferred conditions regarding the amount (added amount) of the hydrosilane compound (D) used in the reaction step, the type of solvent used in the reaction step, and the reaction temperature are the same as those shown in the embodiment of "the step of carrying out a hydrosilanization reaction of an allyl compound (C) and a hydrosilane compound (D) in the presence of a ruthenium complex (A)". The preferred amount (added amount) of the ruthenium compound (A') is the same as the amount (added amount) of the ruthenium complex (A) described above. In this manufacturing method, the following operation is included: mixing the ruthenium compound (A') and compound (B) in a reaction tank to generate the ruthenium complex (A) in the system. Therefore, for example, it is preferable to add the ruthenium compound (A') and compound (B) while stirring the allyl compound (C) added to the reaction tank at a given temperature, followed by the addition of the hydrosilane compound (D). There is no particular limitation on the time interval from the addition of ruthenium compound (A') and compound (B) until the addition of hydrosilane compound (D), which can be appropriately determined based on the introduction rate of the target silane and the manufacturing time.

[0084] The amount of compound (B) added is not particularly limited, but relative to the allyl compound (C), it is usually 0.01 ppm or more by weight, preferably 0.1 ppm or more, more preferably 1 ppm or more, usually 10% or less, preferably 1% or less, more preferably 0.1% or less.

[0085] According to the method for manufacturing the silyl-containing compound (E) described above, a mixture comprising the silyl-containing compound (E) and a ruthenium complex (A) can be obtained. In particular, the mixture comprises an organic polymer (E) as a silyl-containing compound. a A polymer mixture of a hydrolyzable silyl group and a ruthenium complex (A) can be used to form a curable composition by mixing a curing catalyst into the mixture.

[0086] In the aforementioned polymer mixture, the content of ruthenium complex (A) is determined according to the amount of ruthenium complex (A) or ruthenium compound (A') used (added amount). Specifically, relative to the polymer containing hydrolyzable silane, the content of ruthenium complex (A) by weight is typically 0.01 ppm or more, preferably 0.1 ppm or more, more preferably 1 ppm or more, typically 10% or less, preferably 1% or less, more preferably 0.1% or less.

[0087] <Curing Compositions>

[0088] In organic polymers containing silyl groups (E a When the organic polymer containing a hydrolyzable silyl group is used, a curable composition comprising it can be formed. Furthermore, the above-mentioned curable composition can be cured to obtain a cured product. As a silyl-containing organic polymer (E...a The polymer backbone of the polymer is as described above, more preferably a polyoxyolefin polymer, and even more preferably polyoxypropylene.

[0089] Compared to organic polymers containing hydrolyzable silanes produced using conventionally known hydrosilylation catalysts such as Karstedt catalysts, the curable composition containing the hydrolyzable silane-containing organic polymer obtained by the manufacturing method described above exhibits excellent curability due to its shorter surface curing time. Furthermore, the cured product obtained by curing this composition exhibits high modulus and high strength.

[0090] (Catalyst solidification)

[0091] With the aim of promoting the hydrolysis / condensation reaction of hydrolyzable silyl groups, i.e., to promote the curing reaction, the curing composition of this embodiment preferably contains a curing catalyst.

[0092] As a solidification catalyst, conventionally known solid catalysts can be used, specifically organotin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, alkoxy metals, inorganic acids, mixtures thereof, etc.

[0093] Specific examples of organotin compounds include: dibutyltin dilaurate, dibutyltin dioctanoate, bis(butylmaleic acid) dibutyltin, dibutyltin diacetate, dibutyltin oxide, bis(acetylacetone) dibutyltin, reactants of dibutyltin oxide with silicate compounds, reactants of dibutyltin oxide with phthalates, dioctyltin diacetate, dioctyltin dilaurate, bis(ethylmaleic acid) dioctyltin, bis(octylmaleic acid) dioctyltin, dioctyltin bis(acetylacetone), dioctyltin distearate, dioctyltin oxide, and reactants of dioctyltin oxide with silicate compounds. Considering the increased environmental concerns of recent years, dioctyltin compounds are preferred.

[0094] Specific examples of metal salts of carboxylic acids include: tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and calcium carboxylate. The following carboxylic acids can be combined with various metals as the carboxylic acid group.

[0095] Specific examples of amine compounds include: amines such as octylamine, 2-ethylhexylamine, laurylamine, stearylamine, piperidine, 4-methylpiperidine, and hexamethyleneimine; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, and diphenylguanidine; biguanides such as butylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; and ketimine compounds.

[0096] Specific examples of carboxylic acids include: acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and 2-ethylhexanoic acid (versatic acid).

[0097] Specific examples of alkoxy metals include: titanium compounds such as tetrabutyl titanate, tetra(acetylacetone)titanium, ethyl acetoacetate titanium, and diisopropoxytitanium bis(ethyl acetoacetate); aluminum compounds such as tri(acetylacetone)aluminum and diisopropoxyaluminum ethyl acetoacetate; and zirconium compounds such as tetra(acetylacetone)zirconium.

[0098] Other curing catalysts can also be compounds containing fluorine anions, photoacid generators, and photoalkali generators.

[0099] Curing catalysts can combine two or more different catalysts. For example, by combining the above-mentioned amine compounds with carboxylic acids or amine compounds with alkoxy metals, it may be possible to obtain an effect of improved reactivity.

[0100] The amount of the curing catalyst used is relative to the silyl-containing organic polymer (E) in this embodiment. a The amount is 100 parts by weight, preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, and particularly preferably 0.01 to 10 parts by weight. Furthermore, in the curing catalyst, after the curing composition has cured, it sometimes seeps to the surface of the cured material and contaminates the surface. In such cases, by setting the amount of curing catalyst used to 0.01 to 3.0 parts by weight, curability can be ensured, and the surface condition of the cured material can be well maintained.

[0101] In the curable composition of this embodiment, other additives may include: silicon compounds, tackifiers, plasticizers, solvents, diluents, silicates, fillers, anti-sagging agents, antioxidants, light stabilizers, ultraviolet absorbers, property modifiers, tackifying resins, epoxy-containing compounds, photocurable substances, oxygen-curable substances, surface modifiers, epoxy resins, other resins, flame retardants, and foaming agents. Furthermore, in the curable composition of this embodiment, various additives may be added as needed to adjust the various properties of the composition or cured product. Examples of such additives include: curing property modifiers, free radical inhibitors, metal passivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, and fungicides.

[0102] (filler)

[0103] Various fillers can be incorporated into the curable composition of this embodiment. Examples of fillers include: heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium dioxide, fumed silica, precipitated silica, crystalline silica, fused silica, silicic anhydride, hydrated silicic acid, carbon black, iron oxide, aluminum micropowder, zinc oxide, activated zinc oxide, PVC powder, PMMA powder, glass fiber and filaments, etc.

[0104] Compared to the silyl-containing organic polymer (E) of this embodiment a 100 parts by weight, preferably 1 to 300 parts by weight, more preferably 10 to 250 parts by weight.

[0105] To reduce the weight (density) of the composition, organic or inorganic hollow spheres can be added. Hollow spheres are spherical fillers with a hollow interior. Examples of materials for these hollow spheres include inorganic materials such as glass, white sand, and silica, as well as organic materials such as phenolic resin, urea resin, polystyrene, and saline.

[0106] Compared to the silyl-containing organic polymer (E) of this embodiment a 100 parts by weight, preferably 0.1 to 100 parts by weight, more preferably 1 to 20 parts by weight.

[0107] (Thickening agent)

[0108] A tackifier may be added to the curable composition of this embodiment. As a tackifier, a silane coupling agent or a reactant of a silane coupling agent may be added.

[0109] Specific examples of silane coupling agents include: γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, and other amino-containing silanes; γ-isocyanate propyltrimethoxysilane, γ-isocyanate propyltrimethoxysilane, etc. This includes isocyanate-containing silanes such as hydroxyl silanes, γ-isocyanate propylmethyl dimethoxysilane, α-isocyanate methyl trimethoxysilane, and α-isocyanate methyl dimethoxymethylsilane; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyl dimethoxysilane; and epoxy-containing silanes such as γ-glycidyl etheroxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Additionally, condensates of various silane coupling agents, such as aminosilane condensates and condensates of aminosilanes with other alkoxysilanes, and reactants of various silane coupling agents, such as reactants of aminosilanes and epoxysilanes, and reactants of aminosilanes and (meth)acrylate silanes, can also be used. Only one of the above-mentioned thickeners can be used, or two or more can be used in combination.

[0110] Compared to the silyl-containing organic polymer (E) of this embodiment a The amount of silane coupling agent used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight.

[0111] (Plasticizer)

[0112] Plasticizers may be added to the curable composition of this embodiment. Specific examples of plasticizers include: phthalate compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; terephthalate compounds such as bis(2-ethylhexyl) phthalate; and non-phthalate compounds such as diisononyl 1,2-cyclohexanedicarboxylate. Ester compounds; aliphatic polycarboxylic acid ester compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, and tributyl acetylacetonate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylacetonate; alkyl sulfonates; phosphate ester compounds; trimellitic acid ester compounds; chlorinated paraffins; hydrocarbon oils such as alkyl biphenyls and partially hydrogenated terphenyls; processing oils; epoxidized soybean oil, benzyl epoxidized stearate, and other epoxy plasticizers.

[0113] Alternatively, polymeric plasticizers can be used. Specific examples of polymeric plasticizers include: vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol with a number average molecular weight of 500 or higher, and derivatives obtained by converting the hydroxyl groups of these polyether polyols into ester groups, ether groups, etc.; polystyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, etc. Plasticizers can be used alone or in combination of two or more.

[0114] Furthermore, polymeric plasticizers may or may not contain reactive silyl groups. When reactive silyl groups are present, they function as reactive plasticizers, preventing the transfer of plasticizer from the cured product. In the case of reactive silyl groups, it is preferable that there are 1 or less per molecule, more preferably 0.8 or less. Plasticizers containing reactive silyl groups, particularly when using oxidized olefin polymers containing reactive silyl groups, preferably have a number average molecular weight lower than that of silyl-containing organic polymers (E...). a ).

[0115] Compared to the silyl-containing organic polymer (E) of this embodiment a The amount of 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.

[0116] (Solvent, diluent)

[0117] Solvents or diluents may be added to the curable composition of this embodiment. There are no particular limitations on the solvents and diluents; aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers, etc., may be used. When using solvents or diluents, considering the issue of air pollution when using the composition 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-mentioned solvents or diluents may be used alone or in combination of two or more.

[0118] (Anti-sagging agent)

[0119] In the curable composition of this embodiment, an anti-sagging agent can be added as needed to prevent sagging and improve workability. There are no particular limitations on the anti-sagging agent; examples include: polyamide waxes; hydrogenated castor oil derivatives; and metallic soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sagging agents can be used alone or in combination of two or more.

[0120] Compared to the silyl-containing organic polymer (E) of this embodiment aThe preferred amount of anti-sagging agent is 0.1 to 20 parts by weight per 100 parts by weight.

[0121] (Antioxidants)

[0122] Antioxidants (anti-aging agents) can be used in the curable composition of this embodiment. Using antioxidants can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. Examples include: Irganox 245, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 1330, and Irganox 1520 (all manufactured by BASF); SONGNOX 1076 (manufactured by SONGWON); and BHT. Similarly, hindered amine light stabilizers as shown in Tinuvin 622LD, Tinuvin 144, Tinuvin 292; Chimassorb 944LD, Chimassorb 119FL (all manufactured by BASF); ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63, ADK STAB LA-68 (all manufactured by ADEKA Corporation); Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all manufactured by Sankyo Lifetech Corporation); and NocRac CD (manufactured by Ouchi Shinsei Chemical Co., Ltd.) can also be used. Other antioxidants such as SONGNOX 4120, Naugard 445, and OKABEST CLX050 can also be used. Specific examples of antioxidants are described in Japanese Patent Application Publication Nos. 4-283259 and 9-194731.

[0123] Compared to the silyl-containing organic polymer (E) of this embodiment a 100 parts by weight, the amount of antioxidant used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight.

[0124] (Light stabilizer)

[0125] A light stabilizer can be used in the curable composition of this embodiment. Using a light stabilizer can prevent photo-oxidative degradation of the cured product. Examples of light stabilizers include benzotriazoles, hindered amines, and benzoate compounds, with hindered amines being particularly preferred.

[0126] Compared to the silyl-containing organic polymer (E) of this embodiment a100 parts by weight, the amount of light stabilizer used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight.

[0127] (UV absorber)

[0128] Ultraviolet absorbers can be used in the curable composition of this embodiment. Using ultraviolet absorbers can improve the surface weather resistance of the cured product. Examples of ultraviolet absorbers include benzophenones, benzotriazoles, salicylates, substituted acrylonitriles, and metal chelates, with benzotriazoles being particularly preferred. Examples include commercially available brands such as Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571, Tinuvin 1600, and Tinuvin B75 (all manufactured by BASF).

[0129] Compared to the silyl-containing organic polymer (E) of this embodiment a 100 parts by weight, the amount of ultraviolet absorber used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight.

[0130] (Modifier)

[0131] In the curable composition of this embodiment, a property modifier can be added as needed to adjust the tensile properties of the cured product. There are no particular limitations on the property modifier, but examples include: alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane and phenyltrimethoxysilane; alkylisopropoxysilanes such as dimethyldiisopropoxysilane, methyltriisopropoxysilane, and γ-glycidoxypropylmethyldiisopropoxysilane; trialkylsilyl borates such as tri(trimethylsilyl)borate and tri(triethylsilyl)borate; organosilicon varnishes; polysiloxanes, etc. By using the above-mentioned property modifiers, the hardness of the curable composition of this embodiment during curing can be increased, or conversely, the hardness can be decreased, and the elongation at break can be increased. The above-mentioned property modifiers can be used alone or in combination of two or more.

[0132] In particular, compounds that generate monovalent silanol groups within the molecule through hydrolysis have the effect of reducing the modulus of the cured material without exacerbating surface stickiness. Compounds that generate trimethylsilanol are especially preferred. Examples of compounds that generate monovalent silanol groups within the molecule through hydrolysis include derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerol, pentaerythritol, and sorbitol, which are organosilicon compounds that generate monosilane alcohols through hydrolysis. Specifically, examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.

[0133] Compared to the silyl-containing organic polymer (E) of this embodiment a 100 parts by weight, the amount of the property modifier used is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight.

[0134] (Tackifying resin)

[0135] To improve adhesion and bonding to the substrate, or as needed, a tackifying resin may be added to the curable composition of this embodiment. There are no particular limitations on the tackifying resin; commonly used tackifying resins can be used.

[0136] Specific examples include: terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenolic resins, phenolic resins, modified phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins, coumarone-indene resins, rosin resins, rosin resins, hydrogenated rosin resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and their hydrogenates, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, and DCPD resins. These resins can be used alone or in combination of two or more.

[0137] Compared to the silyl-containing organic polymer (E) of this embodiment a The amount of tackifying 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.

[0138] (Compounds containing epoxy groups)

[0139] In the curable composition of this embodiment, compounds containing epoxy groups can be used. Using compounds with epoxy groups can improve the restitution properties of the cured product. Examples of compounds with epoxy groups include: epoxidized unsaturated oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown as epichlorohydrin derivatives, and mixtures thereof. Specifically, examples include: epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylic acid ester (E-PS), octyl epoxy stearate, butyl epoxy stearate, etc. Compared to the silyl-containing organic polymers (E-PS) of this embodiment... a 100 parts by weight, the epoxy compound can be used in the range of 0.5 to 50 parts by weight.

[0140] (Photocurable substances)

[0141] In the curable composition of this embodiment, a photocurable substance can be used. When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured material, which can improve the stickiness and weather resistance of the cured material. Such compounds include various substances such as organic monomers, oligomers, resins, or compositions containing them. As representative photocurable substances, monomers, oligomers, or mixtures thereof having one or more unsaturated groups of acrylic or methacrylic acid, i.e., unsaturated acrylic compounds, polyvinyl cinnamate, or azide resins, etc., can be used.

[0142] Compared to the silyl-containing organic polymer (E) of this embodiment a The amount of photocurable material used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight.

[0143] (Oxygen-curing substances)

[0144] Oxygen-curing substances can be used in the curing composition of this embodiment. Examples of oxygen-curing substances include unsaturated compounds that react with oxygen in the air, forming a cured film near the surface of the cured material, thus preventing surface stickiness and the adhesion of dust and dirt to the surface of the cured material. Specific examples of oxygen-curing substances include: drying oils such as tung oil and linseed oil; various alkyd resins obtained by modifying these compounds; acrylic polymers, epoxy resins, and silicone resins modified from drying oils; and liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, and C5-C8 dienes obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene. These can be used alone or in combination of two or more.

[0145] Compared to the silyl-containing organic polymer (E) of this embodiment a The amount of oxygen-curing substance used is preferably in the range of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight. As described in Japanese Patent Application Publication No. 3-160053, the oxygen-curing substance can be used in combination with the light-curing substance.

[0146] (Epoxy resin)

[0147] Epoxy resins can be used in combination in the curable composition of this embodiment. Compositions containing epoxy resins are particularly preferred as adhesives, especially as adhesives for exterior wall tiles. Examples of epoxy resins include bisphenol A type epoxy resins and phenolic varnish type epoxy resins.

[0148] Epoxy resin and the silyl-containing organic polymer (E) of this embodiment a The preferred usage ratio is based on the weight percentage of silyl-containing organic polymers (E). a The range of epoxy resin is 100 / 1 to 1 / 100.

[0149] When epoxy resin is added, a curing agent for curing epoxy resin can be used in combination with the curable composition of this embodiment. There are no particular limitations on the epoxy resin curing agent that can be used; commonly used epoxy resin curing agents can be employed.

[0150] When using an epoxy resin curing agent, the amount used is preferably in the range of 0.1 to 300 parts by weight relative to 100 parts by weight of epoxy resin.

[0151] <<Preparation of Curable Compositions>>

[0152] The curing composition of this embodiment can be prepared as a single-component form in which all the compounding components are pre-mixed and sealed, and cured by moisture in the air after application. Alternatively, it can be prepared as a two-component form, in which a curing catalyst, filler, plasticizer, water, and other components are pre-mixed as curing agents, and this compounding material is mixed with the organic polymer composition before use. From an operability point of view, the single-component form is preferred.

[0153] In the case of a single-component curable composition, since all the compounding components are pre-combined, it is preferable to pre-dehydrate and dry the compounding components containing moisture before use, or to dehydrate them during compounding by means of reduced pressure. In addition to dehydration and drying, storage stability can be further improved by adding alkoxysilane compounds such as methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-glycidoxypropyltrimethoxysilane.

[0154] <Applications>

[0155] The curable composition of this embodiment can be used as an adhesive, a sealing material for buildings / ships / automobiles / roads, a bonding agent, a waterproofing material, a waterproof coating material, a release agent, a vibration damping material, a sound insulation material, a foaming material, a coating, and a spraying material. The cured product obtained by curing the curable composition of this embodiment has excellent flexibility and adhesion, and therefore can be appropriately used as a sealing material or an adhesive.

[0156] Furthermore, the curable composition of this embodiment can be used in electrical / electronic component materials such as solar cell back sealant, electrical / electronic component and device electrical insulation materials such as wire / cable insulation covering material, acoustic insulation materials, elastic adhesives, adhesives, contact adhesives, spray sealants, crack repair materials, tile adhesives, asphalt waterproofing adhesives, powder coatings, casting materials, medical rubber materials, medical adhesives, medical adhesive sheets, medical device sealing materials, dental impression materials, food packaging materials, wall panels, etc. This product has various applications, including: sealing materials for seams in packaging materials; coating materials; anti-slip covering materials; cushioning materials; primers; conductive materials for electromagnetic wave shielding; thermally conductive materials; hot-melt materials; adhesives for electrical and electronic applications; films; gaskets; concrete reinforcing materials; adhesives for temporary fixation; various molding materials; rust-proofing / waterproofing sealants for the ends (cut sections) of wire-embedded glass and laminated glass; liquid sealants used in automotive parts, truck and bus parts, train parts, aircraft parts, ship parts, motor parts, and various machine parts. In the automotive industry, for example, it can be used for bonding and installing plastic covers, trim pieces, flanges, bumpers, window mounts, interior parts, and exterior parts. Furthermore, because it can adhere to a wide range of substrates, such as glass, porcelain, wood, metal, and resin molded materials, either alone or with the aid of a primer, it can also be used in various types of sealing and adhesive compositions. Furthermore, the curable composition of this embodiment can also be used as an adhesive for interior trim panels, exterior trim panels, tile laying, stone laying, ceiling finishes, floor finishes, wall finishes, vehicle panels, electrical / electronic / precision instrument assembly, adhesives for bonding leather, fiber products, fabrics, paper, boards, and rubber, reactive post-crosslinking pressure-sensitive adhesives, sealants for direct glazing, sealants for multi-layered glass, sealants for SSG construction methods, sealants for construction joints in buildings, and materials for civil engineering and bridges. Additionally, it can be used as an adhesive material for adhesive tapes, adhesive sheets, etc.

[0157] Preferred embodiments of this disclosure are set forth in the following items, but the invention is not limited to the following items.

[0158] [Project 1]

[0159] A ruthenium complex (A) having compound (B) as a ligand, wherein,

[0160] Compound (B) has at least one carbon-carbon double bond in a molecule, and at least one carbon atom in the carbon-carbon double bond is bonded with an electron-withdrawing group.

[0161] [Project 2]

[0162] According to the ruthenium complex (A) described in Project 1, wherein,

[0163] Compound (B) has a benzene ring skeleton as the skeleton containing the carbon-carbon double bond.

[0164] [Project 3]

[0165] According to the ruthenium complex (A) described in Project 1, wherein,

[0166] Compound (B) has a norbornene skeleton as the skeleton containing the carbon-carbon double bond.

[0167] [Project 4]

[0168] The ruthenium complex (A) according to any one of items 1 to 3, wherein,

[0169] The electron-withdrawing group is selected from at least one of fluorine, bromine, and iodine groups.

[0170] [Project 5]

[0171] According to the ruthenium complex (A) described in Project 2, wherein,

[0172] Compound (B) is selected from at least one of 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene and 1,3,5-tribromobenzene.

[0173] [Project 6]

[0174] According to the ruthenium complex (A) described in Project 3, wherein,

[0175] Compound (B) is 2,3-dibromonorbornene.

[0176] [Project 7]

[0177] A catalyst for a hydrosilylation reaction comprising the ruthenium complex (A) described in any one of items 1 to 6.

[0178] [Project 8]

[0179] A method for manufacturing a silyl-containing compound (E), comprising:

[0180] The process of carrying out a hydrosilylation reaction by mixing an allyl compound (C), a hydrosilane compound (D), and the hydrosilylation reaction catalyst described in Project 7.

[0181] [Project 9]

[0182] According to the manufacturing method described in Project 8, wherein...

[0183] In the hydrogen silanization reaction, compound (B) is further mixed.

[0184] [Project 10]

[0185] A manufacturing method for a silyl-containing compound (E), the method comprising:

[0186] The process of carrying out a hydrosilylation reaction by mixing an allyl compound (C), a hydrosilane compound (D), a ruthenium compound (A') without compound (B) as a ligand, and compound (B).

[0187] Compound (B) has at least one carbon-carbon double bond in one molecule, and at least one carbon atom in the carbon-carbon double bond is bonded with an electron-withdrawing group.

[0188] [Project 11]

[0189] The manufacturing method according to any one of items 8 to 10, wherein,

[0190] The amount of hydrosilane compound (D) used is 3 molar equivalents or more, relative to the allyl group in the allyl-containing compound (C).

[0191] [Project 12]

[0192] The manufacturing method according to any one of items 8 to 11, wherein,

[0193] The silyl-containing compound (E) is a polymer with a number average molecular weight exceeding 3000.

[0194] [Project 13]

[0195] The manufacturing method according to any one of items 8 to 12, wherein,

[0196] The silyl-containing compound (E) is a polymer containing hydrolyzable silyl groups.

[0197] [Project 14]

[0198] According to the manufacturing method described in item 13, wherein...

[0199] The silyl-containing compound (E) is a polyoxyethylene polymer containing hydrolyzable silyl groups.

[0200] [Project 15]

[0201] The manufacturing method according to any one of items 8 to 14, wherein,

[0202] Compound (B) has a benzene ring skeleton as the skeleton containing the carbon-carbon double bond.

[0203] [Project 16]

[0204] The manufacturing method according to any one of items 8 to 14, wherein,

[0205] Compound (B) has a norbornene skeleton as the skeleton containing the carbon-carbon double bond.

[0206] [Project 17]

[0207] The manufacturing method according to any one of items 8 to 16, wherein,

[0208] The electron-withdrawing group is selected from at least one of fluorine, bromine, or iodine groups.

[0209] [Project 18]

[0210] According to the manufacturing method described in item 15, wherein...

[0211] Compound (B) is selected from at least one of 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene and 1,3,5-tribromobenzene.

[0212] [Project 19]

[0213] According to the manufacturing method described in item 16, wherein,

[0214] Compound (B) is 2,3-dibromonorbornene.

[0215] [Project 20]

[0216] The manufacturing method according to any one of items 10 to 19, wherein,

[0217] The ruthenium compound (A') has ligands selected from 2,5-norbornadiene, benzene, and p-cymene.

[0218] [Project 21]

[0219] A polymer mixture comprising: a polymer containing hydrolyzable silane and a ruthenium complex (A) as described in any one of items 1 to 6.

[0220] [Project 22]

[0221] A curable composition comprising the polymer mixture described in item 21 and a curing catalyst.

[0222] [Project 23]

[0223] A cured product obtained by curing the curable composition described in item 22.

[0224] Example

[0225] The following examples illustrate the present invention in further detail, but the present invention is not limited to these examples.

[0226] The number-average molecular weights in the examples are GPC molecular weights measured under the following conditions.

[0227] Liquid delivery system: Tosoh HLC-8420GPC

[0228] Pillar: Tosoh TSKgel SuperH series

[0229] Solvent: THF (tetrahydrofuran)

[0230] Molecular weight: Polystyrene conversion

[0231] Measurement temperature: 40℃

[0232] The proportions of silyl, 1-propenyl, or hydride were calculated using nuclear magnetic resonance (NMR) equipment as described below. 1 The measurements were performed using HNMR.

[0233] Device: AVANCE III HD500 digital device (manufactured by BRUKER)

[0234] (Example 1)

[0235] An ethanol solution containing 0.15 g of ruthenium(III) chloride hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) as ruthenium compound (A') was stirred under a nitrogen atmosphere. Simultaneously, 0.064 g of sodium carbonate and 0.20 g of 2,3-dibromonorbornene (manufactured by Tokyo Chemical Industry Co., Ltd.) as compound (B) were added under reflux. After stirring for 1 hour under the above conditions, the mixture was filtered and dried under reduced pressure to obtain ruthenium complex (A-1) as ruthenium complex (A).

[0236] (Example 2)

[0237] While stirring an ethanol solution containing 0.15 g of ruthenium(III) chloride hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) as ruthenium compound (A') under a nitrogen atmosphere, 0.064 g of sodium carbonate and 0.36 g of 2,3-dibromonorbornene (manufactured by Tokyo Chemical Industry Co., Ltd.) as compound (B) were added under reflux. After stirring for 1 hour under the above conditions, the mixture was filtered and dried under reduced pressure to obtain ruthenium complex (A-2) as ruthenium complex (A).

[0238] (Synthesis example 1)

[0239] For a hydroxyl-terminated polyoxypropylene polymer (F-1) with a number-average molecular weight of approximately 3100, 1.1 molar equivalents of sodium methoxide were added in the form of a 28% methanol solution relative to the hydroxyl groups of polymer (F-1). After removing the methanol by vacuum distillation, 1.3 molar equivalents of allyl chloride were added relative to the hydroxyl groups of polymer (F-1), and the reaction was carried out at 130°C for 1 hour to convert the terminal hydroxyl groups to allyl groups. Subsequently, unreacted allyl chloride was removed by vacuum degassing. The resulting unpurified allyl-terminated polyoxypropylene was mixed with n-hexane and water, stirred, and the water was removed by centrifugation. Hexane was then removed from the resulting hexane solution by vacuum distillation, thereby removing the metal salt from the polymer. Through the above operations, an allyl-containing organic polymer (C-1) was obtained as an allyl compound (C). The number-average molecular weight of this polymer is 3100.

[0240] (Example 3)

[0241] For the polymer (C-1) containing an allyl compound (C), 2400 ppm of the ruthenium complex (A-1) obtained in Example 1 as the ruthenium complex (A) and dimethoxymethylsilane as the hydrosilane compound (D) (in 5.0 molar equivalents relative to the allyl group present in the polymer (C-1)) were added, and a hydrosilylation reaction was carried out at 70°C. The reaction was carried out every 1 hour from the start of the reaction. 1 ¹H NMR analysis was performed, and the reaction continued until the allyl group of the polymer (C-1) could be confirmed to be completely consumed. The volatile components were then distilled under reduced pressure to obtain a polymer as a silyl-containing compound (E). The obtained polymer was analyzed by… 1 ¹H NMR was used to determine the proportions of each group relative to the total of silyl, 1-propenyl, and hydrides. The results are shown in Table 1.

[0242] (Example 4)

[0243] Using 2400 ppm of the ruthenium complex (A-2) obtained in Example 2 as ruthenium complex (A), the hydrosilylation reaction was carried out by the same method as in Example 3. The results are shown in Table 1.

[0244] (Examples 5-17)

[0245] For polymer (C-1), which is an allyl compound (C), as described in Table 1, a ruthenium complex (A) or each ruthenium compound (A'), and each compound (B) were added, and the mixture was stirred at 70°C for 10 minutes. Furthermore, dimethoxymethylsilane (in 5.0 molar equivalents relative to the allyl group in polymer (C-1)) was added as a hydrosilane compound (D), and a hydrosilylation reaction was carried out on the allyl group in polymer (C-1) at 70°C. The reaction was carried out every 1 hour from the start of the reaction.1 ¹H NMR analysis was performed until the allyl group of the polymer (C-1) was completely consumed. After the reaction, the volatile components were removed by vacuum distillation to obtain a polymer as a silyl-containing compound (E). The obtained polymer was then subjected to… 1 ¹H NMR was used to determine the proportions of each group relative to the total of silyl, 1-propenyl, and hydrides. The results are shown in Table 1.

[0246]

[0247] (Comparative Examples 1-6)

[0248] For polymer (C-1) containing an allyl compound (C), as described in Table 2, a commercially available Karstedt catalyst (a platinum-divinyldisiloxane complex (in isopropanol solution, converted to platinum equivalents of 3% by weight)) or 2400 ppm of each ruthenium compound (A'), and dimethoxymethylsilane as a hydrosilane compound (D) (in 5.0 molar equivalents relative to the allyl group in polymer (C-1)) were added, and the allyl group in polymer (C-1) was subjected to a hydrosilylation reaction at 70°C. The reaction was carried out every 1 hour from the start of the reaction. 1 H NMR analysis was performed, and the reaction continued until the allyl group of the polymer (C-1) was completely consumed. The volatile components were then removed by vacuum distillation to obtain a silyl-containing polymer. The resulting polymer was then subjected to... 1 ¹H NMR was used to determine the proportions of each group relative to the total of silyl, 1-propenyl, and hydrides. The results are shown in Table 2.

[0249] (Comparative Examples 7-12)

[0250] For the polymer (C-1) containing an allyl compound (C), as described in Table 2, [RuCl2(nbd)], which is a ruthenium compound (A'), is added. n (nbd: norbornene) 2400 ppm, and each compound (B') not belonging to compound (B), were stirred at 70 °C for 10 minutes. Furthermore, dimethoxymethylsilane (in 5.0 molar equivalents relative to the allyl group of polymer (C-1)) was added as a hydrosilane compound (D), and a hydrosilylation reaction was carried out on the allyl group of polymer (C-1) at 70 °C. The reaction was carried out every 1 hour from the start of the reaction. 1 ¹H NMR analysis was performed, and the reaction continued until the allyl group of the polymer (C-1) was completely consumed. The volatile components were then distilled under reduced pressure to obtain a silyl-containing polymer. The obtained polymer was then subjected to… 1¹H NMR was used to determine the proportions of each group relative to the total of silyl, 1-propenyl, and hydrides. The results are shown in Table 2.

[0251]

[0252] The following information is available from Tables 1 and 2. Comparing Examples 3 and 4 with Comparative Examples 1-6, it is evident that in Examples 3 and 4, which used a ruthenium complex (A) containing compound (B) as a ligand, compared to Comparative Examples 1-6 which used a Karstedt catalyst or ruthenium compound (A'), the polymers obtained using these examples had a higher proportion of silyl groups and a lower proportion of 1-propenyl and hydrides. Therefore, silyl groups can be introduced with greater selectivity for the allyl group of polymer (C-1). Comparing Examples 3 and 4, it is evident that Example 4, which used a ruthenium complex (A-2), had a higher silyl group introduction rate. Therefore, it is preferable to use more compound (B) when synthesizing the ruthenium complex (A).

[0253] Furthermore, when comparing Examples 3 and 5, which used ruthenium complex (A-1), it can be seen that Example 5, which added 2,3-dibromonorbornene as compound (B) in addition to ruthenium complex (A-1), can introduce silanes with greater selectivity.

[0254] Furthermore, when comparing Examples 6-17, which used ruthenium compound (A') and further added compound (B), with Comparative Examples 2-6, which used ruthenium compound (A') but did not add compound (B), it was found that Examples 6-17 could introduce silane groups with higher selectivity for the allyl group of polymer (C-1). In this way, the simpler method of adding compound (B) to ruthenium compound (A') followed by hydrosilylation without using a pre-synthesized ruthenium complex (A) also significantly improves the silane introduction rate.

[0255] Additionally, [RuCl2(nbd)] will be used. n Example 6 uses [RuCl2(nbd)] as a ruthenium compound (A') and further adds 2,3-dibromonorbornadiene as compound (B). n When comparing Comparative Examples 7-12, which consist of ruthenium compound (A') and further compound (B') not belonging to compound (B), it was found that Example 6 could introduce silane with higher selectivity for the allyl group of polymer (C-1). No increase in silane introduction rate was observed in Comparative Examples 7-12 compared to Comparative Example 2, while Example 6 showed a significant increase in silane introduction rate compared to Comparative Example 2. Therefore, the addition of compound (B) with a specific structure is important for increasing the silane introduction rate.

[0256] (Synthesis example 2)

[0257] Polyoxypropylene glycol with a number average molecular weight of approximately 4500 was used as an initiator to polymerize propylene oxide using zinc hexacyanocobaltate glycol dimethyl ether complex catalyst, resulting in a hydroxyl-containing organic polymer (F-2) with a number average molecular weight of 14500 and hydroxyl groups at both ends.

[0258] For the hydroxyl-containing organic polymer (F-2), 1.1 molar equivalents of sodium methoxide were added in the form of a 28% methanol solution relative to the hydroxyl groups of polymer (F-2). After distilling off the methanol by vacuum distillation, 1.3 molar equivalents of allyl chloride were added relative to the hydroxyl groups of polymer (F-2), and the reaction was carried out at 130°C for 1 hour. The allyl chloride was then distilled off by vacuum distillation. The resulting unpurified allyl-containing organic polymer was mixed with n-hexane and water and stirred. The water was removed by centrifugation, and the metal salt in the polymer was removed by vacuum distillation from the resulting hexane solution. Through the above operations, an allyl-containing organic polymer (C-2) was obtained as an allyl compound (C). The number average molecular weight of this polymer was 14500.

[0259] (Example 18)

[0260] For polymer (C-2), which is an allyl compound (C), 240 ppm of ruthenium complex (A-2) obtained in Example 2 as ruthenium complex (A) was added, and dimethoxymethylsilane (in 5.0 molar equivalents relative to the allyl group of polymer (C-2)) as hydrosilane compound (D) was further added, and a hydrosilylation reaction was carried out on the allyl group of polymer (C-2) at 90°C. The reaction was carried out every 1 hour from the start of the reaction. 1 H NMR analysis was performed, and the reaction continued until the allyl group of the polymer (C-2) was completely consumed. The volatile components were then removed by vacuum distillation to obtain a polymer as a silyl-containing compound (E). The obtained polymer was then subjected to... 1 ¹H NMR was used to determine the proportions of each group relative to the total of silyl, 1-propenyl, and hydrides. The results are shown in Table 3.

[0261] (Example 19)

[0262] For the polymer (C-2) containing an allyl compound (C), [RuCl2(nbd)] is added as a ruthenium compound (A'). n240 ppm of 2,3-dibromonorbornene, as compound (B), and 620 ppm of 2,3-dibromonorbornene were added, and the mixture was stirred at 90 °C for 10 minutes. Furthermore, dimethoxymethylsilane (in 5.0 molar equivalents relative to the allyl group of polymer (C-2)) was added as hydrosilane compound (D), and the allyl group of polymer (C-2) was subjected to a hydrosilylation reaction at 90 °C. The reaction was carried out every 1 hour from the start of the reaction. 1 H NMR analysis was performed, and the reaction continued until the allyl group of the polymer (C-2) was completely consumed. The volatile components were then distilled under reduced pressure to obtain a polymer as a silyl-containing compound (E). The obtained polymer was then subjected to... 1 ¹H NMR was used to determine the proportions of each group relative to the total of silyl, 1-propenyl, and hydrides. The results are shown in Table 3.

[0263] (Compare Examples 13 and 14)

[0264] For polymers (C-2) containing allyl compounds (C), [RuCl2(nbd)] is added as a Karstedt catalyst or a ruthenium compound (A'). n 240 ppm of dimethoxymethylsilane (in 5.0 molar equivalents relative to the allyl group of polymer (C-2)) was further added as hydrosilane compound (D), and the allyl group of polymer (C-2) was subjected to a hydrosilylation reaction at 90 °C. The reaction was carried out every 1 hour from the start of the reaction. 1 H NMR analysis showed that the reaction proceeded until the allyl group in the polymer (C-2) was completely consumed, and then the volatile components were distilled under reduced pressure to obtain a silyl-containing polymer. The obtained polymer was then analyzed by... 1 ¹H NMR was used to determine the proportions of each group relative to the total of silyl, 1-propenyl, and hydrides. The results are shown in Table 3.

[0265]

[0266] As can be clearly seen from Table 3, compared with Comparative Examples 13 and 14 which used the Karstedt catalyst or the ruthenium compound (A'), in Example 18 which used the ruthenium complex (A) and Example 19 which used the ruthenium compound (A') and compound (B), silyl groups can be introduced with higher selectivity for the allyl group of polymer (C-2). Therefore, it can be confirmed that even for polymer (C) with a number average molecular weight of 14,500, a high silyl group introduction rate can be achieved by using the manufacturing method of the present invention for hydrosilylation reaction.

[0267] (Synthesis example 3)

[0268] Polyoxypropylene glycol with a number average molecular weight of approximately 4500 was used as an initiator to polymerize propylene oxide using zinc hexacyanocobaltate glycol dimethyl ether complex catalyst, resulting in a hydroxyl-containing organic polymer (F-3) with a number average molecular weight of 27600 and hydroxyl groups at both ends.

[0269] For the hydroxyl-containing organic polymer (F-3), 1.1 molar equivalents of sodium methoxide were added in the form of a 28% methanol solution relative to the hydroxyl groups of polymer (F-3). After removing the methanol by vacuum distillation, 1.3 molar equivalents of allyl chloride were added relative to the hydroxyl groups of polymer (F-3), and the reaction was carried out at 130°C for 1 hour. The allyl chloride was then distilled under vacuum. The resulting unpurified allyl-containing organic polymer was mixed with n-hexane and water and stirred. The water was then removed by centrifugation, and the metal salt in the polymer was removed from the resulting hexane solution by vacuum distillation of hexane. Through these operations, an allyl-containing organic polymer (C-3) was obtained as an allyl compound (C). The number average molecular weight of this polymer was 27,600.

[0270] (Example 20)

[0271] For polymer (C-3), which is an allyl compound (C), 240 ppm of ruthenium complex (A-2) obtained in Example 2 as ruthenium complex (A) and dimethoxymethylsilane as hydrosilane compound (D) (in 5.0 molar equivalents relative to the allyl group of polymer (C-3)) were added, and a hydrosilylation reaction was carried out on the allyl group of polymer (C-3) at 90°C. The reaction was carried out every 1 hour from the start of the reaction. 1 ¹H NMR analysis was performed, and the reaction continued until the allyl group of the polymer (C-3) was completely consumed. The volatile components were then distilled under reduced pressure to obtain a silyl-containing compound (E). The resulting polymer was then subjected to… 1 ¹H NMR measurements were performed to calculate the proportions of each group relative to the total of silyl, 1-propenyl, and hydrides. The results are shown in Table 4.

[0272] (Examples 21-25)

[0273] For polymer (C-3), which is an allyl compound (C), as described in Table 4, each ruthenium compound (A') and each compound (B) were added, and the mixture was stirred at 90°C for 10 minutes. Furthermore, dimethoxymethylsilane (in 5.0 molar equivalents relative to the allyl group in polymer (C-3)) was added as a hydrosilane compound (D) to perform a hydrosilylation reaction on the allyl group in polymer (C-3) at 90°C. The reaction was carried out every 1 hour from the start of the reaction. 1H NMR analysis was performed, and the reaction continued until the allyl group of the polymer (C-3) was completely consumed. The volatile components were then distilled under reduced pressure to obtain a polymer as a silyl-containing compound (E). The obtained polymer was then subjected to... 1 ¹H NMR measurements were performed to calculate the proportions of each group relative to the total of silyl, 1-propenyl, and hydrides. The results are shown in Table 4.

[0274] (Comparative Examples 15-17)

[0275] For polymer (C-3), which is an allyl compound (C), a hydrosilylation reaction was carried out on the allyl groups of polymer (C-3) at 90°C by adding 240 ppm of commercially available Karstedt catalyst or each ruthenium compound (A') and dimethoxymethylsilane as a hydrosilane compound (D) (in 5.0 molar equivalents relative to the allyl groups of polymer (C-3)). 1 ¹H NMR analysis was performed, and the reaction continued until the allyl group of the polymer (C-3) was completely consumed. The volatile components were then distilled under reduced pressure to obtain a silyl-containing polymer. The obtained polymer was then subjected to… 1 HNMR measurements were performed to calculate the proportions of each group relative to the total of silyl, 1-propenyl, and hydrides. The results are shown in Table 4.

[0276]

[0277] As can be clearly seen from Table 4, in Examples 20-25, compared to Comparative Examples 15-17, silane alkyl groups can be introduced into the allyl groups of the allyl-containing organic polymers with higher selectivity. Therefore, it can be confirmed that even for polymer (C) with a number average molecular weight of 27,600, a high silane alkyl introduction rate can be achieved by using the manufacturing method of the present invention to perform the hydrosilylation reaction.

[0278] (Example 26)

[0279] For the polymer (C-2) obtained in Synthesis Example 2, which is an allyl compound (C), [RuCl2(nbd)], which is a ruthenium compound (A'), was added. n 240 ppm of 2,3-dibromonorbornene and 620 ppm of 2,3-dibromonorbornene as compound (B) were added, and the mixture was stirred at 100 °C for 10 minutes. Furthermore, triethoxysilane (in 5.0 molar equivalents relative to the allyl group of polymer (C-2)) was added as hydrosilane compound (D), and the allyl group of polymer (C-2) was subjected to a hydrosilylation reaction at 100 °C. The reaction was carried out every 1 hour from the start of the reaction. 1H NMR analysis was performed, and the reaction continued until the allyl group of the polymer (C-2) was completely consumed. The volatile components were then distilled under reduced pressure to obtain a polymer as a silyl-containing compound (E). The obtained polymer was then subjected to... 1 ¹H NMR measurements were performed to calculate the proportions of each group relative to the total of silyl, 1-propenyl, and hydrides. The results are shown in Table 5.

[0280] (Comparative Example 18)

[0281] The polymer (C-2) containing the allyl compound (C) obtained in Synthesis Example 2 was stirred at 100°C while [RuCl2(nbd)], as the ruthenium compound (A'), was added. n 240 ppm of triethoxysilane (in 5.0 molar equivalents relative to the allyl group of polymer (C-2)) was added as a hydrosilane compound (D), and the allyl group of polymer (C-2) was subjected to a hydrosilylation reaction at 100 °C. After reacting for 5 hours from the start of the reaction, the volatile components were distilled under reduced pressure to obtain a silane-containing polymer. The obtained polymer was then subjected to... 1 ¹H NMR measurements were performed to calculate the proportions of each group relative to the total of silyl, 1-propenyl, and hydrides. The results are shown in Table 5.

[0282]

[0283] As can be clearly seen from Table 5, in Example 26, the allyl group of the allyl-containing organic polymer can be selectively introduced with silane compared to Comparative Example 18. Therefore, it can be confirmed that even for another hydrosilane compound, a high silane introduction rate can be achieved by using the manufacturing method of the present invention to carry out the hydrosilylation reaction.

[0284] (Example 27)

[0285] For 1-octene (1.0 g, 8.9 mmol), which is an allyl-containing compound (C), 2 mg of ruthenium complex (A-2), which is the ruthenium complex (A) obtained in Example 2, was added while stirring at 60 °C. Additionally, dimethoxymethylsilane (1.4 g, 13.4 mmol), which is a hydrosilane compound (D), was added, and the allyl group of 1-octene was subjected to a hydrosilylation reaction at 60 °C. 1 ¹H NMR analysis confirmed that the allyl group in 1-octene was completely consumed within 30 minutes, resulting in the formation of a silane with a yield of over 99%. Therefore, the manufacturing method of the present invention can be applied without problems even when the allyl-containing compound (C) is a low-molecular-weight compound rather than a polymer.

[0286] (Example 28)

[0287] In an atmosphere of 23°C and 50% relative humidity, relative to 100 parts by weight of the hydrolyzable silyl-containing organic polymer (E-1) as the silyl-containing compound (E) obtained in Example 19, 90 parts by weight of DINP (manufactured by J-Plus Co., Ltd.: diisononyl phthalate), 160 parts by weight of Baiyanhua CCR (manufactured by Baishi Calcium Co., Ltd.: precipitated calcium carbonate), 54 parts by weight of Whiton SB (manufactured by Baishi Calcium Co., Ltd.: heavy calcium carbonate), 5 parts by weight of TIPAQUE R820 (manufactured by Ishihara Sangyo Co., Ltd.: titanium dioxide), and Disparlon... Two parts by weight of 6500 (manufactured by Kusumoto Chemical Co., Ltd.: fatty acid amide wax), one part by weight of Tinuvin 326 (manufactured by BASF: 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole), and one part by weight of Tinuvin 770 (manufactured by BASF: bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate) were mixed together, and five parts by weight of A-171 (manufactured by Momentive: vinyltrimethoxysilane), three parts by weight of A-1120 (manufactured by Momentive: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane), and two parts by weight of NEOSTANN U-220H (manufactured by Nitto Chemical Co., Ltd.: dibutyltin bis(acetylacetone)) were added. After thorough mixing with a spatula, the mixture was uniformly mixed and degassed using a rotary mixer to obtain a curable composition.

[0288] (Surface curing time)

[0289] In an atmosphere of 23°C and 50% relative humidity, the obtained curable composition was filled into a mold with a thickness of approximately 5 mm using a spatula. The time it took for the surface to become flat was defined as the curing start time. The time it took for the composition no longer adhered to the evaluation object after touching the surface with the spatula was defined as the surface curing time. The results are shown in Table 6.

[0290] (Dumbbell stretching properties)

[0291] The obtained curable composition was filled into a mold and cured at 23°C and 50% relative humidity for 2 days, followed by curing at 50°C for 2 days, to produce a sheet-like cured material with a thickness of approximately 3 mm. The sheet-like cured material was punched into a No. 3 dumbbell shape, and tensile strength tests were conducted at 23°C and 50% relative humidity. The modulus (M50 and M100) at 50% and 100% tension was determined. In addition, the strength at break (TB) and elongation at break (EB) were determined. The tests were conducted using an Autogragh (AGS-J) from Shimadzu Corporation at a tensile speed of 200 mm / min. The results are shown in Table 6.

[0292] (Example 29)

[0293] 100 parts by weight of a hydrolyzable silyl-containing organic polymer (E-2), which was obtained as the silyl-containing compound (E) in Example 20, were used instead of 100 parts by weight of the hydrolyzable silyl-containing organic polymer (E-1). Otherwise, a curable composition was obtained by the same method as in Example 28. The surface curing time and dumbbell tensile properties were evaluated using the obtained curable composition in the same manner as in Example 28. The results are shown in Table 6.

[0294] (Comparative Example 19)

[0295] 100 parts by weight of the hydrolyzable silyl-containing organic polymer (E'-1) obtained in Comparative Example 13 were used instead of 100 parts by weight of the hydrolyzable silyl-containing organic polymer (E-1), and otherwise, a curable composition was obtained by the same method as in Example 28. The surface curing time and dumbbell tensile properties were evaluated using the obtained curable composition in the same manner as in Example 28. The results are shown in Table 6.

[0296] (Comparative Example 20)

[0297] 100 parts by weight of the hydrolyzable silyl-containing organic polymer (E'-2) obtained in Comparative Example 15 were used instead of 100 parts by weight of the hydrolyzable silyl-containing organic polymer (E-1), and otherwise, a curable composition was obtained by the same method as in Example 28. The surface curing time and dumbbell tensile properties were evaluated using the obtained curable composition in the same manner as in Example 28. The results are shown in Table 6.

[0298]

[0299] As shown in Table 6, compared to the hydrolyzable silyl-containing organic polymer (E'-1) manufactured using the same allyl-containing organic polymer (C-2) as a raw material and a Karstedt catalyst, the hydrolyzable silyl-containing organic polymer (E-1) obtained by the manufacturing method of the present invention exhibits a shorter surface curing time and better curability. Furthermore, the modulus and strength increase, with M100 increasing by approximately 1.6 times and strength by approximately 1.1 times. Additionally, compared to the hydrolyzable silyl-containing organic polymer (E'-2) manufactured using the same allyl-containing organic polymer (C-3) as a raw material and a Karstedt catalyst, the hydrolyzable silyl-containing organic polymer (E-2) obtained by the manufacturing method of the present invention exhibits a shorter surface curing time and better curability. Furthermore, the modulus and strength increase, with M100 increasing by approximately 1.7 times and strength by approximately 1.3 times.

[0300] (Synthesis Example 4)

[0301] For the hydroxyl-containing organic polymer (F-3) obtained in Synthesis Example 3, 0.9 molar equivalents of sodium methoxide were added in the form of a 28% methanol solution relative to the hydroxyl groups of polymer (F-3). After removing the methanol by vacuum distillation, 1.2 molar equivalents of 3-chloro-2-methyl-1-propene (methylallyl chloride) were added in the form of a 28% methanol solution relative to the hydroxyl groups of polymer (F-3). The reaction was carried out at 130°C for 1 hour to convert the terminal hydroxyl groups to methylallyl groups. Then, the 3-chloro-2-methyl-1-propene (methylallyl chloride) was distilled under vacuum. Subsequently, 0.6 molar equivalents of sodium methoxide were added in the form of a 28% methanol solution relative to the hydroxyl groups of polymer (F-3). After removing methanol by vacuum distillation, 0.7 molar equivalents of 3-chloro-2-methyl-1-propene (methylallyl chloride) were added relative to the hydroxyl groups of polymer (F-3), and the reaction was carried out at 130°C for 1 hour to convert the residual terminal hydroxyl groups to methylallyl groups. Then, 3-chloro-2-methyl-1-propene (methylallyl chloride) was distilled under vacuum. The resulting unpurified methylallyl-containing organic polymer was mixed with n-hexane and water and stirred. Water was removed by centrifugation, and hexane was distilled under vacuum from the resulting hexane solution to remove the metal salt from the polymer. Through these operations, a methylallyl-containing organic polymer (G-1) was obtained as the methylallyl-containing compound (G).

[0302] For a methylallyl-containing organic polymer (G-1), 100 ppm of Karstedt catalyst and 1000 ppm of 2,5-di-tert-butyl-1,4-benzoquinone were added, followed by the addition of dimethoxymethylsilane as the hydrosilane compound (D) (in 1.5 molar equivalents relative to the methylallyl groups in polymer (G-1)). The methylallyl groups in polymer (G-1) were then subjected to a hydrosilylation reaction at 100 °C. The reaction was carried out every 1 hour from the start of the reaction. 1 H NMR analysis was performed until the methyl allyl group of polymer (G-1) was completely consumed, and then the volatile components were distilled under reduced pressure to obtain a silyl-containing polymer (E'-3).

[0303] (Example 30)

[0304] A single-component curable composition was prepared using a 5L planetary mixer (manufactured by Dalton Corporation) according to the composition shown in Table 7. First, 160 parts by weight of Ultra-Pflex (manufactured by Specialty Minerals: colloidal calcium carbonate), 54 parts by weight of Q3T (manufactured by Huber Corporation: untreated heavy calcium carbonate), and 20 parts by weight of Ti-Pure R-902+ (manufactured by Chemours: titanium dioxide) were dried under reduced pressure at 120°C for 2 hours. Next, 100 parts by weight of the hydrolyzable silyl-containing organic polymer (E-3) obtained in Example 22 as the silyl-containing compound (E), 90 parts by weight of DINP (manufactured by J-Plus Co., Ltd.: diisononyl phthalate), 2 parts by weight of Crayvallac SL (manufactured by ARKEMA: fatty acid amide wax), 1 part by weight of Tinuvin 328 (manufactured by BASF: ultraviolet absorber), and 1 part by weight of Tinuvin 770 (manufactured by BASF: light stabilizer) were added to a mixer and mixed for 10 minutes. The resulting mixture was removed, passed through a 3-roll mill once to ensure uniform dispersion, and then the mixture was put back into the mixer for dehydration under reduced pressure for 2 hours. After dehydration under reduced pressure, the mixture was cooled to below 50°C. Three parts by weight of A-171 (manufactured by Momentive: vinyltrimethoxysilane), three parts by weight of A-1120 (manufactured by Momentive: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane), and two parts by weight of NEOSTANNU-220H (manufactured by Nitto Chemical Co., Ltd.: dibutyltin bis(acetylacetone)) were added and mixed for 3 minutes. Then, degassing under reduced pressure was performed for 2 minutes. The resulting mixture was immediately filled into a moisture-proof aluminum cylinder and sealed, thus obtaining a cured composition.

[0305] (Surface curing time)

[0306] In an atmosphere of 23°C and 50% relative humidity, the obtained curable composition was filled into a mold with a thickness of approximately 5 mm using a spatula. The time it took for the surface to become flat was defined as the curing start time. The time it took for the composition no longer adhered to the evaluation object to be touched by the spatula was defined as the surface curing time. The results are shown in Table 7.

[0307] (Dumbbell stretching properties)

[0308] The obtained curable composition was filled into a mold and cured at 23°C and 50% relative humidity for 3 days, followed by curing at 50°C for 4 days to produce a sheet-like cured material with a thickness of approximately 3 mm. The sheet-like cured material was punched into a No. 3 dumbbell shape, and tensile strength tests were conducted at 23°C and 50% relative humidity. The modulus (M50 and M100) at 50% and 100% tension was determined. In addition, the strength at break (TB) and elongation at break (EB) were determined. The tests were conducted using an Autogragh (AGS-J) from Shimadzu Corporation at a tensile speed of 200 mm / min. The results are shown in Table 7.

[0309] (Tear strength)

[0310] The obtained curable composition was filled into a 3 mm thick sheet mold at 23°C and 50% relative humidity. It was cured for 3 days at 23°C and 50% relative humidity, and then aged in a dryer at 50°C for 4 days to obtain a sheet-like cured product. The cured product was punched into dumbbell shapes (JIS Type A) for tear testing to obtain test pieces. Using the obtained test pieces, tear tests were performed using Autogragh at 23°C and 50% relative humidity (tensile speed 200 mm / min), and the stress at break (TB) was determined.

[0311] (Tensile shear strength)

[0312] At 23°C and 50% relative humidity, aluminum was used as the substrate. The aforementioned curable composition was applied to a bonding area of ​​25mm × 25mm and a thickness of 50μm. After a 2-minute exposure period, the substrates were bonded together. The resulting test specimens were then placed under constant temperature and humidity conditions of 23°C and 50%. Tensile shear tests (tensile speed 50mm / min) were performed using Autogragh after 1 hour, 3 hours, and 24 hours, and the stress at fracture (TB) was measured.

[0313] In addition, the obtained test specimens were cured at 23°C and 50% relative humidity for 3 days, and further cured at 50°C for 4 days. Tensile shear tests were then performed using Autogragh to determine the stress at fracture (TB). Furthermore, the strength performance rate at each time point was calculated as described below.

[0314] Strength performance rate (%) = (shear strength at each time point) ÷ (shear strength after curing at 23℃ and 50% relative humidity for 3 days, followed by further curing at 50℃ for 4 days) × 100

[0315] The results are shown in Table 7.

[0316] (Comparative Example 21)

[0317] 100 parts by weight of the hydrolyzable silyl-containing organic polymer (E'-2) obtained in Comparative Example 15 were used instead of 100 parts by weight of the hydrolyzable silyl-containing organic polymer (E-3), and otherwise, a curable composition was obtained by the same method as in Example 30. Using the obtained curable composition, the surface curing time, dumbbell tensile properties, tear strength, and tensile shear strength were evaluated in the same manner as in Example 30. The results are shown in Table 7.

[0318] (Comparative Example 22)

[0319] 100 parts by weight of the hydrolyzable silyl-containing organic polymer (E'-3) obtained in Synthesis Example 4 were used instead of 100 parts by weight of the hydrolyzable silyl-containing organic polymer (E-3), and otherwise, a curable composition was obtained by the same method as in Example 30. Using the obtained curable composition, the surface curing time, dumbbell tensile properties, tear strength, and tensile shear strength were evaluated in the same manner as in Example 30. The results are shown in Table 7.

[0320]

[0321] As shown in Table 7, compared with the hydrolyzable silyl-containing organic polymer (E'-2) and the hydrolyzable silyl-containing organic polymer (E'-3) produced using the same allyl-containing organic polymer (C-3) as a raw material and the Karstedt catalyst, the hydrolyzable silyl-containing organic polymer (E-3) obtained by the manufacturing method of the present invention exhibits a shorter surface curing time and better curability. Furthermore, it exhibits better tear strength and tensile shear strength. Regarding the hydrolyzable silyl-containing organic polymer (E-3), in the dumbbell tensile test, it shows higher modulus and strength compared to the hydrolyzable silyl-containing organic polymer (E'-2), and shows values ​​at the same level as the hydrolyzable silyl-containing organic polymer (E'-3).

[0322] (Examples 31-34)

[0323] For polymers (C-3) containing allyl compounds (C), as described in Table 8, [RuCl2(nbd)] is added as a ruthenium compound (A'). n100 ppm of 2,3-dibromonorbornene as compound (B) and 260 ppm of 2,3-dibromonorbornene were added, and the mixture was stirred for 10 minutes at the reaction temperature described in Table 8. Furthermore, dimethoxymethylsilane as hydrosilane compound (D) (in molar equivalents relative to the allyl groups present in polymer (C-3) as described in Table 8) was added to induce a hydrosilylation reaction of the allyl groups present in polymer (C-3). The reaction was carried out every 1 hour from the start of the reaction. 1 H NMR analysis was performed, and the reaction continued until the allyl group of the polymer (C-3) was completely consumed. The volatile components were then distilled under reduced pressure to obtain a polymer as a silyl-containing compound (E). The obtained polymer was then subjected to... 1 ¹H NMR was used to determine the proportions of each group relative to the total of silyl, 1-propenyl, and hydrides. The viscosity of the polymer was measured using a viscometer RE85U (manufactured by Toki Sangyo Co., Ltd.) at 23°C. The results are shown in Table 8.

[0324]

[0325] As can be clearly seen from Table 8, silane groups can be introduced with high selectivity in Examples 31-34. In particular, it is evident that the higher the molar equivalent of the hydrosilane compound (D) with allyl groups relative to the polymer (C-3), the higher the silane introduction rate, and the lower the viscosity of the organic polymer containing hydrolyzable silane groups.

[0326] In Example 31, a hydrosilane compound (D) having an allyl group equivalent of 5 moles relative to polymer (C-3) was reacted with a polymer that had the highest silanization rate and the lowest viscosity as shown in Table 8.

[0327] In Example 32, which reacted with a hydrosilane compound (D) having an allyl group equivalent of 3 moles relative to the polymer (C-3), although the silanization rate decreased and the viscosity increased after silanization compared to Example 31, a polymer with lower viscosity was obtained compared to Example 33, which reacted with a hydrosilane compound (D) having an allyl group equivalent of 2 moles relative to the polymer (C-3).

Claims

1. A ruthenium complex (A) having a compound (B) as a ligand, wherein, Compound (B) has at least one carbon-carbon double bond in a molecule, and at least one carbon atom in the carbon-carbon double bond is bonded with an electron-withdrawing group.

2. The ruthenium complex (A) according to claim 1, wherein, Compound (B) has a benzene ring skeleton as the skeleton containing the carbon-carbon double bond.

3. The ruthenium complex (A) according to claim 1, wherein, Compound (B) has a norbornene skeleton as the skeleton containing the carbon-carbon double bond.

4. The ruthenium complex (A) according to any one of claims 1 to 3, wherein, The electron-withdrawing group is selected from at least one of fluorine, bromine, and iodine groups.

5. The ruthenium complex (A) according to claim 2, wherein, Compound (B) is selected from at least one of 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene and 1,3,5-tribromobenzene.

6. The ruthenium complex (A) according to claim 3, wherein, Compound (B) is 2,3-dibromonorbornene.

7. A catalyst for a hydrosilylation reaction comprising the ruthenium complex (A) of claim 1.

8. A method for manufacturing a silyl-containing compound (E), comprising: The process of carrying out a hydrosilylation reaction by mixing an allyl compound (C), a hydrosilane compound (D), and the hydrosilylation reaction catalyst according to claim 7.

9. The manufacturing method according to claim 8, wherein, In the hydrogen silanization reaction, compound (B) is further mixed.

10. A method for manufacturing a silyl-containing compound (E), the method comprising: The process of carrying out a hydrosilylation reaction by mixing an allyl compound (C), a hydrosilane compound (D), a ruthenium compound (A') without compound (B) as a ligand, and compound (B). Compound (B) has at least one carbon-carbon double bond in one molecule, and at least one carbon atom in the carbon-carbon double bond is bonded with an electron-withdrawing group.

11. The manufacturing method according to any one of claims 8 to 10, wherein, The amount of hydrosilane compound (D) used is 3 molar equivalents or more, relative to the allyl group in the allyl-containing compound (C).

12. The manufacturing method according to any one of claims 8 to 10, wherein, The silyl-containing compound (E) is a polymer with a number average molecular weight exceeding 3000.

13. The manufacturing method according to any one of claims 8 to 10, wherein, The silyl-containing compound (E) is a polymer containing hydrolyzable silyl groups.

14. The manufacturing method according to claim 13, wherein, The silyl-containing compound (E) is a polyoxyethylene polymer containing hydrolyzable silyl groups.

15. The manufacturing method according to any one of claims 8 to 10, wherein, Compound (B) has a benzene ring skeleton as the skeleton containing the carbon-carbon double bond.

16. The manufacturing method according to any one of claims 8 to 10, wherein, Compound (B) has a norbornene skeleton as the skeleton containing the carbon-carbon double bond.

17. The manufacturing method according to any one of claims 8 to 10, wherein, The electron-withdrawing group is selected from at least one of fluorine, bromine, or iodine groups.

18. The manufacturing method according to claim 15, wherein, Compound (B) is selected from at least one of 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene and 1,3,5-tribromobenzene.

19. The manufacturing method according to claim 16, wherein, Compound (B) is 2,3-dibromonorbornene.

20. The manufacturing method according to claim 10, wherein, The ruthenium compound (A') has ligands selected from 2,5-norbornadiene, benzene, and p-cymene.

21. A polymer mixture comprising: a polymer containing a hydrolyzable silyl group and a ruthenium complex (A) according to any one of claims 1 to 3.

22. A curable composition comprising the polymer mixture of claim 21 and a curing catalyst.

23. A cured product obtained by curing the curable composition of claim 22.

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