Method for producing reactive silicon group-containing organic polymers

Abstract

To provide a method for producing a reactive silicon group-containing organic polymer that can promote hydrosilylation and can also improve storage stability of polymers.SOLUTION: A method for producing a reactive silicon group-containing organic polymer includes a process for adding a cocatalyst A that includes a Group 8 metal catalyst and a carboxylic acid compound, and a halogenated silane compound represented by the formula (1), to react an unsaturated group-containing organic polymer with a silylating agent; or a process for adding a cocatalyst B that includes the Group 8 metal catalyst and the carboxylic acid compound but does not include the halogenated silane compound, to react the unsaturated group-containing organic polymer with the silylating agent, followed by addition of the halogenated silane compound. The formula (1) is: XmSiR14-m [where, X represents a halogen atom, m represents an integer of 1-3, and R1 represents a C1-20 monovalent organic group other than hydrolyzable groups].SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a method for producing a reactive silicon group-containing organic polymer. [Background technology]

[0002] Polymers containing reactive silicon groups are known to have the property of crosslinking even at room temperature through the formation of siloxane bonds accompanied by hydrolysis reactions of the reactive silicon groups due to moisture, etc., resulting in a rubbery cured product.

[0003] Among these polymers containing reactive silicon groups, oxyalkylene polymers, saturated hydrocarbon polymers, alkyl acrylate polymers, and alkyl methacrylate polymers are already produced industrially and are widely used in applications such as sealants, adhesives, and paints. Polymers containing reactive silicon groups undergo silanol condensation reactions with other polymers to increase their molecular weight and form crosslinked structures.

[0004] Polymers containing reactive silicon groups are produced, for example, by first producing a polymer with an unsaturated group as a terminal group, and then hydrosilylating it using a silylating agent. However, hydrosilylating reactions involve many side reactions, and there is a problem that reactive silicon groups are not introduced to all terminal groups, resulting in a decrease in the silylation rate, which is the proportion of reactive silicon groups in the terminal groups. Therefore, methods for accelerating hydrosilylating reactions have been studied, and it is known that adding a carboxylic acid compound to the group 8 metal catalyst used in the hydrosilylating reaction improves the silylation rate (for example, Patent Documents 1 and 2). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2000-95785 [Patent Document 2] Japanese Patent Publication No. 2000-143679 [Overview of the Initiative]

Problems to be Solved by the Invention

[0006] However, in the hydrosilylation reaction, when a carboxylic acid compound is added to a Group 8 metal catalyst, the carboxylic acid compound acts as an acid catalyst for the dealcohol condensation reaction, and the viscosity of the polymer increases during storage, resulting in a problem of reduced storage stability. The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a reactive silicon group-containing organic polymer that can promote the hydrosilylation reaction, suppress an increase in the viscosity of the polymer during storage, and improve the storage stability.

Means for Solving the Problems

[0007] The present invention is as follows [1] to [5]. [1] A cocatalyst A containing a Group 8 metal catalyst, a carboxylic acid compound, and a halogenated silane compound represented by the following formula (1) is added, and an unsaturated group-containing organic polymer and a silylating agent are reacted, or a cocatalyst B containing the Group 8 metal catalyst and the carboxylic acid compound and not containing the halogenated silane compound is added, and after reacting the unsaturated group-containing organic polymer and the silylating agent, the halogenated silane compound is added, to produce a reactive silicon group-containing organic polymer represented by the following formula (2). X 1 , 2 SiR 1 4-m Formula (1) -SiR 2 a Z 3-a Formula (2) [In formula (1), X is a halogen atom, m is an integer of 1 to 3, and R 1 is a monovalent organic group having 1 to 20 carbon atoms and represents an organic group other than a hydrolyzable group. When m is 1 or 2, R 1 may be the same as or different from each other. When m is 2 or 3, X may be the same as or different from each other. In formula (2), R 2 ​is a monovalent organic group having 1 to 20 carbon atoms and represents an organic group other than a hydrolyzable group. Z represents a halogen atom, a hydroxyl group, or a hydrolyzable group. a is an integer of 0 to 2. When a is 2, R 2 may be the same as or different from each other. When a is 0 or 1, Z may be the same as or different from each other.] [2] A method for producing a reactive silicon group-containing organic polymer according to [1], wherein the Group 8 metal catalyst has at least one metal selected from the group consisting of cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum. [3] A method for producing a reactive silicon group-containing organic polymer according to [1] or [2], wherein the halogenated silane compound is chlorotrimethylsilane. [4] A method for producing a reactive silicon group-containing organic polymer according to any one of [1] to [3], wherein the reactive silicon group-containing organic polymer is a polymer having a unit based on an oxyalkylene monomer. [5] A method for producing a reactive silicon group-containing organic polymer according to any one of [1] to [3], wherein the reactive silicon group-containing organic polymer is a polymer having a unit based on an alkyl acrylate monomer or an alkyl methacrylate monomer. [Effect of the Invention]

[0008] According to the present invention, there can be provided a method for producing a reactive silicon group-containing organic polymer that can promote a hydrosilylation reaction, suppress an increase in the viscosity of the polymer during storage, and improve storage stability. [Embodiments for Carrying Out the Invention]

[0009] The meanings and definitions of the terms in this specification are as follows. The numerical range represented by "~" means a numerical range having the numerical values before and after ~ as the lower limit value and the upper limit value. The "unit" constituting the polymer means an atomic group directly formed by the polymerization of monomers. The "oxyalkylene polymer" is a polymer composed of a main chain and end groups. The "main chain" in the oxyalkylene polymer includes the residue of the initiator and repeating units (polyoxyalkylene chains) based on the oxyalkylene monomer. The "end group" in the oxyalkylene polymer means an atomic group containing the oxygen atom closest to the molecular end among the oxygen atoms in the polyoxyalkylene chain. However, when the atomic group contains the residue of the initiator, it is not regarded as an end group. The "(meth)acrylic acid ester polymer" means a polymer having one or both of a polymer chain formed from repeating units based on an acrylic acid alkyl ester monomer and a polymer chain formed from repeating units based on a methacrylic acid alkyl ester monomer. The "(meth)acrylic acid" means one or both of acrylic acid and methacrylic acid. The "unsaturated group" means a monovalent group containing an unsaturated carbon-carbon double bond or a carbon-carbon triple bond at the molecular end. The "carboxylic acid compound" means a compound having a carboxy group.

[0010] The "silylation rate" can be measured by NMR analysis and is determined by the following formula. Silylation rate = number of reactive silicon groups / [number of reactive silicon groups + (number of carbon-carbon double bonds) + (number of carbon-carbon triple bonds) × 2]

[0011] The number average molecular weight (Mn) and mass average molecular weight (Mw) in this specification are polystyrene equivalent molecular weights measured using gel permeation chromatography (GPC) with tetrahydrofuran as the eluent and creating a calibration curve using a polystyrene polymer with a known molecular weight. The molecular weight distribution (Mw / Mn) is the ratio of Mw to Mn.

[0012] ≪Method for Producing a Reactive Silicon Group-Containing Organic Polymer≫ The method for producing a reactive silicon group-containing organic polymer according to the first embodiment of the present invention involves adding a group 8 metal catalyst and a co-catalyst A containing a carboxylic acid compound and a halogenated silane compound represented by formula (1) described later, and reacting the unsaturated group-containing organic polymer with a silylating agent. A method for producing a reactive silicon group-containing organic polymer according to a second embodiment of the present invention involves adding a co-catalyst B containing a group 8 metal catalyst and a carboxylic acid compound, reacting the unsaturated group-containing organic polymer with a silylating agent, and then adding the halogenated silane compound. The reactive silicon group-containing organic polymers produced by the manufacturing methods of the first and second embodiments contain a reactive silicon group represented by formula (2) described below. The following describes each component, but the unsaturated group-containing organic polymer, silylating agent, group 8 metal catalyst, reaction conditions, and reactive silicon group-containing organic polymer (including reactive silicon groups) are common to the manufacturing methods of the first and second embodiments.

[0013] <Unsaturated group-containing organic polymer> Examples of organic polymers containing unsaturated groups include, but are not limited to, polyether polymers containing unsaturated groups and vinyl polymers containing unsaturated groups. Examples of unsaturated group-containing polyether polymers include unsaturated group-containing oxyalkylene polymers. Examples of unsaturated group-containing vinyl polymers include unsaturated group-containing (meth)acrylic acid ester polymers.

[0014] The Mn of the unsaturated group-containing organic polymer is preferably 500 to 200,000, and the Mw / Mn ratio is preferably 1.80 or less. The number of unsaturated groups in one molecule of the unsaturated group-containing organic polymer is preferably 1.0 to 8.0, and more preferably 1.0 to 6.0.

[0015] (Unsaturated group-containing oxyalkylene polymer) An unsaturated group-containing oxyalkylene polymer is a polymer having repeating units based on an unsaturated group and an oxyalkylene monomer. The unsaturated group-containing oxyalkylene polymer consists of a main chain and terminal groups. The main chain has repeating units based on initiator residues and oxyalkylene monomers, and the terminal groups have unsaturated groups. Preferably, the main chain consists of repeating units based on initiator residues and oxyalkylene monomers, and the terminal groups have an oxygen atom and an unsaturated group. Examples of oxyalkylene monomers include ethylene oxide monomer, propylene oxide monomer, butylene oxide monomer, and tetramethylene oxide monomer. Propylene oxide monomer is preferred. When the polyoxyalkylene chain in the main chain of the unsaturated group-containing oxyalkylene polymer is a copolymer chain of two or more oxyalkylene monomers, it may be a block polymerization chain or a random polymerization chain.

[0016] The number of terminal groups in one molecule of an unsaturated group-containing oxyalkylene polymer is preferably 1 to 8, more preferably 2 to 6, and even more preferably 2 to 4. The number of unsaturated groups in one molecule of the unsaturated group-containing oxyalkylene polymer is preferably 1.0 to 8.0, more preferably 2.0 to 6.0, and even more preferably 2.0 to 4.0. The number of unsaturated groups per terminal group of an unsaturated group-containing oxyalkylene polymer is preferably 0.5 to 4.0, and more preferably 0.6 to 2.0. The Mn of the unsaturated group-containing oxyalkylene polymer is preferably 2,000 to 100,000, and more preferably 5,000 to 50,000. The Mw / Mn ratio of the unsaturated group-containing oxyalkylene polymer is preferably 1.80 or less. More preferably 1.50 or less, even more preferably 1.40 or less, and particularly preferably 1.20 or less.

[0017] (Method for producing unsaturated group-containing oxyalkylene polymers) The method for producing unsaturated group-containing oxyalkylene polymers can be conventionally known, and the polymer can be produced by ring-opening addition polymerization of one or more oxyalkylene monomers with an initiator, and then converting the hydroxyl groups at the terminal groups of the resulting polymer to alkenyloxy or alkynyloxy groups. Conventional known auxiliary materials such as initiators required for polymerization can also be used, and reaction conditions such as reaction temperature and reaction pressure can be appropriately selected. When using one or more oxyalkylene monomers as initiators for ring-opening addition polymerization, conventionally known catalysts can be used as ring-opening polymerization catalysts. Examples include alkaline catalysts such as KOH, metal compound-porphyrin complex catalysts such as complexes obtained by reacting organoaluminum compounds with porphyrins, complex metal cyanide catalysts, and catalysts consisting of phosphazene compounds. Composite metal cyanide complex catalysts are preferred because they allow for a narrower molecular weight distribution of the polymer, making it easier to obtain a curable composition with low viscosity. Conventional known compounds can be used as the composite metal cyanide complex catalyst, and known methods can also be employed for producing polymers using the composite metal cyanide complex. For example, compounds and production methods disclosed in International Publication No. 2003 / 062301, International Publication No. 2004 / 067633, Japanese Patent Publication No. 2004-269776, Japanese Patent Publication No. 2005-15786, International Publication No. 2013 / 065802, and Japanese Patent Publication No. 2015-010162 can be used. Methods for converting the hydroxyl groups at the end of a polymer to alkenyloxy or alkynyloxy groups include reacting the polymer with an alkali metal salt followed by a halogenated hydrocarbon compound having a carbon-carbon double bond; reacting the polymer with an alkali metal salt followed by an epoxy compound having an unsaturated group, and then reacting it with a halogenated hydrocarbon compound having an unsaturated group; or reacting the polymer with an alkali metal salt followed by a halogenated hydrocarbon compound having a carbon-carbon triple bond.

[0018] (Unsaturated group-containing (meth)acrylic acid ester polymer) An unsaturated group-containing (meth)acrylic acid ester polymer is a polymer having an unsaturated group and repeating units based on an alkyl acrylate monomer or an alkyl methacrylate monomer. The unsaturated group-containing (meth)acrylic acid ester polymer may also have repeating units based on an alkyl acrylate monomer or another monomer copolymerizable with an alkyl methacrylate monomer. As monomers constituting the (meth)acrylic acid ester polymer, for example, conventionally known monomers described in Japanese Patent Publication No. 11-130931 can be used.

[0019] The content of units based on alkyl (meth)acrylate monomers relative to the total monomer units constituting the unsaturated group-containing (meth)acrylate polymer is preferably 50% by mass or more, more preferably 70% by mass or more, and may even be 100% by mass. The number of unsaturated groups in one molecule of the unsaturated group-containing (meth)acrylic acid ester polymer is preferably 1.0 to 8.0, and more preferably 1.0 to 6.0. The Mn of the unsaturated group-containing (meth)acrylic acid ester polymer is preferably 500 to 100,000, and more preferably 1,000 to 80,000. The Mw / Mn ratio of the unsaturated group-containing (meth)acrylic acid ester polymer is preferably 1.80 or less. More preferably 1.50 or less, even more preferably 1.40 or less, and particularly preferably 1.20 or less.

[0020] (Method for producing unsaturated group-containing (meth)acrylic acid ester polymers) Methods for producing unsaturated group-containing (meth)acrylic acid ester polymers can be conventionally known. For example, methods include polymerizing an alkyl (meth)acrylic acid ester monomer with a compound having an unsaturated group and a polymerizable unsaturated bond, or using living radical polymerization to react with a compound having two alkenyl groups at the end of the polymerization reaction. Living radical polymerization is preferred because it yields polymers with arbitrary molecular weights, a narrow molecular weight distribution, and low viscosity. As a living radical polymerization method, for example, atom transfer radical polymerization (ATRP method) is used to polymerize alkyl (meth)acrylate monomers using an organic halide or sulfonyl halogenated compound as an initiator and a transition metal complex as a catalyst. Atom transfer radical polymerization (ATRP method) can be performed using the conventional polymerization method described in Japanese Patent Application Publication No. 11-130931. Unsaturated group-containing (meth)acrylate polymers can be obtained by polymerizing alkyl (meth)acrylate monomers using atom transfer radical polymerization (ATRP method), and then introducing unsaturated groups by reacting them with a compound having at least two alkenyl groups, such as 1,5-hexadiene, 1,7-octadiene, or 1,9-decadiene. In (meth)acrylic acid ester polymers obtained by the ATRP method, the "end group" refers to the group of atoms in the (meth)acrylic acid ester polymer chain that contains the carbon atom closest to the molecular end. If the group of atoms contains an initiator residue, it is not considered an end group.

[0021] <Silylaters> Silylation agents include compounds having both a group that can react with an unsaturated group to form a bond (e.g., a sulfanyl group) and a reactive silicon group represented by formula (2) described below, as well as hydrosilane compounds (e.g., HSiR 2 a Z 3-a , R 2 The definitions of Z and a are the same as in formula (2) described below. Examples include: Specifically, trimethoxysilane, triethoxysilane, triisopropoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, diisopropoxymethylsilane, (α-chloromethyl)dimethoxysilane, and (α-chloromethyl)diethoxysilane. Trimethoxysilane, triethoxysilane, dimethoxymethylsilane, and diethoxymethylsilane are preferred because they have high activity and provide good curability, and dimethoxymethylsilane or trimethoxysilane are more preferred.

[0022] For example, when hydrosilylation of an unsaturated group-containing organic polymer is performed using methyldimethoxysilane, a polymer having a methyldimethoxysilyl group (a type of reactive silicon group) can be obtained. Polymers having reactive silicon groups yield crosslinked bodies through hydrolysis of the silyl group due to moisture in the air, and subsequent silanol condensation reactions with other polymer molecules. Polymers having reactive silicon groups are used in applications requiring weather resistance, heat resistance, and moisture resistance, such as adhesives, sealants, paints, sealants, and waterproofing materials.

[0023] When the unsaturated group of an unsaturated group-containing organic polymer is a carbon-carbon double bond, the amount of silylating agent used is preferably 1 to 20 mol per mol of unsaturated group, and more preferably 1 to 2 mol. When the unsaturated group of an unsaturated group-containing organic polymer is a carbon-carbon triple bond, the amount of silylating agent used is preferably 2 to 40 mol per mol of unsaturated group, and more preferably 2 to 4 mol. Using an amount below the upper limit is preferable because it reduces costs and simplifies the operation of removing the silylating agent after the reaction. Using an amount above the lower limit is preferable because it results in a high silylation rate.

[0024] <Group 8 metal catalyst> A Group 8 metal catalyst is a catalyst containing a metal from Group 8 of the short-period periodic table. The Group 8 metal is preferably at least one metal selected from the group consisting of cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum; more preferably at least one metal selected from the group consisting of ruthenium, palladium, and platinum; and even more preferably platinum. Group 8 metal catalysts can be used as elemental metals, metal salts, or complexes with organic compounds. Specifically, preferred materials include, for example, elemental platinum, platinum metal on a support such as alumina, silica, or carbon black, complexes of chloroplatinic acid with ligands such as alcohols, aldehydes, or ketones, platinum-olefin complexes [e.g., Pt(CH2=CH2)2(PPh3), Pt(CH2=CH2)2Cl2], platinum-acetylacetonate complexes [Pt(C5H7O2)2], platinum-vinylsiloxane complexes [Pt{(vinyl)Me2SiOSiMe2(vinyl)}, Pt{Me(vinyl)SiO}4], platinum-phosphine complexes [Ph(PPh3)4, Pt(PBu3)4], platinum-phosphine complexes [Pt{P(OPh)3}4], and platinum complexes such as these.

[0025] These Group 8 metal catalysts may be used individually or in combination of two or more. Chloroplatinic acid, platinum olefin complexes, platinum-acetylacetonate complexes, and platinum-vinylsiloxane complexes are preferred due to their high reaction activity. Specifically, a solution of hexachloroplatinic acid hexahydrate and platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is preferred. There are no particular restrictions on the amount of Group 8 metal catalyst used, but the amount of Group 8 metal catalyst used for an unsaturated group-containing organic polymer is preferably 1.0 to 20 ppm by mass, and more preferably 1.5 to 10 ppm by mass. If the amount of Group 8 metal catalyst used is above the lower limit of the above range, the hydrosilylation reaction proceeds sufficiently, and if it is below the upper limit of the above range, it is preferable from a cost perspective.

[0026] <Auxiliary catalyst> In the manufacturing method of the first embodiment, co-catalyst A containing a carboxylic acid compound and a halogenated silane compound is used. In the manufacturing method of the second embodiment, co-catalyst B containing a carboxylic acid compound is used.

[0027] <Cocatalyst A> Co-catalyst A contains a carboxylic acid compound and a halogenated silane compound. The carboxylic acid compound and the halogenated silane compound will be described below.

[0028] <Carboxylic acid compounds> The number of carbon atoms in the carboxylic acid compound is preferably between 2 and 17, and more preferably between 3 and 10. Carboxylic acid compounds are compounds that have a carboxyl group, and examples include carboxylic acids and dicarboxylic acids. Preferred carboxylic acids are those having a carbon-carbon double bond at the α-position and those having a carbon-carbon triple bond at the α-position, with carboxylic acids having a carbon-carbon triple bond at the α-position being more preferred. Preferred carboxylic acids include formic acid, acetic acid, trifluoroacetic acid, benzoic acid, crotonic acid, 2-hexenoic acid, phenylpropiolic acid, propiolic acid, 2-butic acid, 2-heptic acid, 2-methyl-3-butic acid, 2-hydroxy-3-butic acid, and 3-butic acid; more preferably formic acid, acetic acid, trifluoroacetic acid, benzoic acid, crotonic acid, and phenylpropiolic acid; and even more preferably phenylpropiolic acid. Examples of dicarboxylic acids include those having a carbon-carbon double bond at the α-position and those having a carbon-carbon triple bond at the α-position. Dicarboxylic acids having a carbon-carbon triple bond at the α-position are preferred. Examples of dicarboxylic acids having a carbon-carbon triple bond at the α-position include those having triple bonds at both α-positions and those having a triple bond at only one α-position, with dicarboxylic acids having triple bonds at both α-positions being more preferred. Acetylenedicarboxylic acids are preferred as dicarboxylic acids.

[0029] The amount of carboxylic acid compound used in co-catalyst A is preferably 0.1 to 20 mol%, and more preferably 1 to 10 mol%, per 1 mol of unsaturated groups in the unsaturated polymer. If the amount is above the lower limit of this range, the silylation rate is further improved. If the amount is below the upper limit of this range, the amount of acid in the solution is suppressed, and thickening is suppressed.

[0030] <Halogenated silane compounds> The halogenated silane compound of co-catalyst A is represented by the following formula (1). X m SiR 1 4-m Formula (1)

[0031] In equation (1) above, X is a halogen atom, m is an integer from 1 to 3, and R 1 This refers to a monovalent organic group having 1 to 20 carbon atoms, excluding hydrolyzable groups. When m is 1 or 2, R 1 The elements may be the same or different from each other. When m is 2 or 3, X may be the same or different from each other. It is preferable that m is 1.

[0032] X is a halogen atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom. R 1 It is preferable that the group is at least one selected from the group consisting of alkyl groups, cycloalkyl groups, alkenyl groups, and aryl groups. It is more preferable that the group is at least one selected from the group consisting of linear or branched alkyl groups having 1 to 4 carbon atoms, cyclohexyl groups, phenyl groups, and benzyl groups. A methyl group or an ethyl group is preferred, and a methyl group is more preferred.

[0033] As the halogenated silane compound, bromosilane compounds and chlorosilane compounds are preferred, and chlorosilane compounds are more preferred. Examples of chlorosilane compounds include chlorotrimethylsilane, chlorotriisopropylsilane, chloroethyldimethylsilane, dimethyl-n-octylchlorosilane, chloro(dodecyl)dimethylsilane, chlorodimethylisopropylsilane, chlorodimethylphenylsilane, and chlorodimethylvinylsilane, with chlorotrimethylsilane being preferred. Examples of bromosilane compounds include bromotrimethylsilane, bromotriisopropylsilane, and bromoethyldimethylsilane.

[0034] Regarding the co-catalyst A, which consists of a carboxylic acid compound and a halogenated silane compound, the mixing ratio of the halogenated silane compound to the carboxylic acid compound is preferably 0.5 to 2.0 in molar ratio, and more preferably 1.0 to 1.5. If the ratio is above the lower limit, the thickening of the polymer is suppressed, and if it is below the upper limit, the hydrosilylation reaction proceeds easily. Carboxylic acid compounds promote the hydrosilylation reaction, while the reaction between the carboxylic acid compound and the halide silane compound generates hydrogen halides. Since the generated hydrogen halides act as a silanol condensation catalyst and increase the viscosity of the polymer, it is preferable to remove them after the hydrosilylation reaction under high temperature and reduced pressure. Because the boiling points of hydrogen halides (hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide) are below room temperature (25°C), they are easily removed at temperatures above room temperature, for example, 50°C or higher, under reduced pressure.

[0035] <Cocatalyst B> Co-catalyst B contains a carboxylic acid compound and does not contain the halogenated silane compound represented by formula (1) above. The carboxylic acid compound contained in co-catalyst B is the same as the carboxylic acid compound listed for co-catalyst A.

[0036] The amount of carboxylic acid compound used as co-catalyst B is preferably 0.1 to 20 mol%, and more preferably 1 to 10 mol%, per 1 mol of unsaturated groups in the unsaturated group-containing polymer. If the amount is above the lower limit of this range, the silylation rate will be further improved. If the amount is below the upper limit of this range, the amount of acid in the solution will be suppressed, and thickening will be suppressed.

[0037] It is preferable to stabilize the Group 8 metal catalyst and co-catalyst by dissolving and diluting them in various solvents, thereby facilitating the handling of the catalyst and co-catalyst. Preferred solvents include, for example, hydrocarbon solvents such as benzene, toluene, and xylene, halogenated hydrocarbons, alcohols, glycols, ethers, esters, ketones, nitriles, and amides. Among these, alcohols, ketones, nitriles, and amides are preferred, with isopropyl alcohol, acetone, N,N-dimethylformamide (DMF), and acetonitrile being more preferred, and acetonitrile being even more preferred. The Group 8 metal catalyst and co-catalyst may be diluted in two or more solvents.

[0038] <Method for adding Group 8 metal catalyst, co-catalyst, and silylating agent in the manufacturing method of the first embodiment> In the first embodiment, co-catalyst A is used. Methods for adding the Group 8 metal catalyst, co-catalyst A, and silylation agent during the hydrosilylation reaction include adding a premix of the Group 8 metal catalyst and co-catalyst A dissolved in the solvent to the reaction solution containing the unsaturated group-containing organic polymer, followed by the addition of the silylation agent for hydrosilylation, or adding each to the reaction solution separately, followed by the addition of the silylation agent for hydrosilylation. Adding the premix to the reaction solution is preferable because it offers the advantage of pre-forming Group 8 metal particle colloids.

[0039] <Method for adding Group 8 metal catalyst, co-catalyst, silylate agent, and halogenated silane compound in the manufacturing method of the second embodiment> In the second embodiment, co-catalyst B is used. Methods for adding the Group 8 metal catalyst, co-catalyst B, and silylation agent during the hydrosilylation reaction include adding a premix of the Group 8 metal catalyst and co-catalyst B dissolved in the solvent to the reaction solution containing the unsaturated group-containing organic polymer, followed by the addition of the silylation agent for hydrosilylation, or adding each to the reaction solution before adding the silylation agent for hydrosilylation. Adding the premix to the reaction solution is preferable because it offers the advantage of pre-forming Group 8 metal particle colloids. Furthermore, in the production method of the second embodiment, a halogenated silane compound is added after the hydrosilylation reaction is complete (after confirming that there is no unreacted silylation agent by NMR analysis). The halogenated silane compound to be added is the same as the halogenated silane compound mentioned for co-catalyst A. In the second embodiment, the molar ratio of the halogenated silane compound to the carboxylic acid compound of co-catalyst B is preferably 0.5 to 2.0, and more preferably 1.0 to 1.5. If it is above the lower limit of this range, the amount of acid in the solution is suppressed, and viscosity is suppressed.

[0040] <Reaction conditions> Hydrosilylation reactions can be carried out in a solvent-free system or in the presence of a solvent. Suitable solvents for hydrosilylation reactions include hydrocarbons, halogenated hydrocarbons, alcohols, ethers, esters, and nitriles, but isopropyl alcohol, heptane, hexane, cyclohexane, benzene, toluene, xylene, and acetonitrile are preferred. Furthermore, since unsaturated group-containing organic polymers are often solids or highly viscous liquids, it is preferable to use a solvent to reduce the viscosity of the reaction solution.

[0041] The reactor gas phase during a hydrosilylation reaction may consist solely of an inert gas such as nitrogen or helium, or it may contain oxygen or other gases. When handling flammable materials during a hydrosilylation reaction, it is preferable to carry out the reaction in the presence of an inert gas such as nitrogen or helium in the reactor gas phase. The presence of oxygen in the gas phase tends to accelerate the hydrosilylation reaction.

[0042] When oxygen is introduced into the gas phase, the hydrosilylation reaction can be carried out in the presence of an antioxidant to suppress oxidation of the reaction solvent. The antioxidant is not particularly limited, but phenolic antioxidants or amine antioxidants that have the function of radical chain inhibitors can be used. Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), tetrakis{methylene-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}methane, and 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane. Examples of amine-based antioxidants that can be used include phenyl-β-naphthylamine, α-naphthylamine, N,N'-di-sec-butyl-p-phenylenediamine, phenothiazine, and N,N'-diphenyl-p-phenylenediamine.

[0043] The hydrosilylation reaction temperature is preferably between 40°C and 150°C, and more preferably between 40°C and 100°C.

[0044] <Reactive silicon group-containing organic polymer> The type of organic polymer, Mn, and Mw / Mn of the reactive silicon group-containing organic polymer are the same as those described for the unsaturated group-containing organic polymer, and the preferred ranges are also the same. The number of reactive silicon groups per molecule is preferably 0.72 to 8.0, and more preferably 0.75 to 6.0. Furthermore, a silylation rate of 72% to 100% is preferred, 75% to 100% is more preferred, 78% to 100% is even more preferred, and 80% to 100% is particularly preferred. The viscosity of the reactive silicon group-containing organic polymer at 25°C is preferably 25 Pa·s or less, more preferably 3 to 25 Pa·s, and even more preferably 4 to 20 Pa·s. If the viscosity of the reactive silicon group-containing organic polymer is above the lower limit of the above range, dripping during work is less likely to occur, and if it is below the upper limit, workability tends to be good.

[0045] <Reactive silicon group-containing oxyalkylene polymer> A reactive silicon group-containing oxyalkylene polymer is a polymer having repeating units based on reactive silicon groups and oxyalkylene monomers. The reactive silicon group-containing oxyalkylene polymer consists of a main chain and terminal groups; the main chain has repeating units based on initiator residues and oxyalkylene monomers, and the terminal groups have reactive silicon groups. Preferably, the main chain consists of repeating units based on initiator residues and oxyalkylene monomers. In the reactive silicon group-containing oxyalkylene polymer, the oxyalkylene monomer, the number of terminal groups in one molecule, Mn, and Mw / Mn are the same as those described for the unsaturated group-containing oxyalkylene polymer, and the preferred ranges are also the same. The number of reactive silicon groups in one molecule of the reactive silicon group-containing oxyalkylene polymer is preferably 0.72 to 8.0, and more preferably 0.8 to 6.0. The number of reactive silicon groups per terminal group of the reactive silicon group-containing oxyalkylene polymer is preferably 0.72 to 4.0, and more preferably 0.75 to 2.0.

[0046] <Reactive silicon group-containing (meth)acrylic acid ester polymer> Reactive silicon group-containing (meth)acrylic acid ester polymers are polymers having repeating units based on reactive silicon groups and alkyl acrylate monomers or alkyl methacrylate monomers. The monomers constituting the reactive silicon group-containing (meth)acrylic acid ester polymer, the number of terminal groups in one molecule, Mn, and Mw / Mn are the same as those described for the unsaturated group-containing (meth)acrylic acid ester polymer. The number of reactive silicon groups in one molecule of the reactive silicon group-containing (meth)acrylic acid ester polymer is preferably 0.72 to 8.0, and more preferably 0.75 to 6.0.

[0047] (Reactive silicon group) Reactive silicon groups have hydrolyzable groups bonded to silicon atoms and can crosslink by forming siloxane bonds. The reaction that forms siloxane bonds is promoted by a curing catalyst. Reactive silicon groups are represented by the following formula (2). -SiR 2 a Z 3-a Formula (2) [In formula (2), R 2 is a monovalent organic group having 1 to 20 carbon atoms, excluding hydrolyzable groups, and Z represents a halogen atom, a hydroxyl group, or a hydrolyzable group. a is an integer from 0 to 2. When a is 2, R 2 The elements may be identical or different from each other, and if a is 0 or 1, Z may be identical or different from each other.

[0048] In equation (2) above, R 2 This represents a monovalent organic group with 1 to 20 carbon atoms. 2 It does not contain hydrolyzable groups. R 2 Preferably, it is at least one selected from the group consisting of hydrocarbon groups having 1 to 20 carbon atoms and triorganosiloxy groups.

[0049] R 2It is preferable that the group is at least one selected from the group consisting of alkyl groups, cycloalkyl groups, aryl groups, α-chloroalkyl groups, and triorganosiloxy groups. It is more preferable that the group is at least one selected from the group consisting of linear or branched alkyl groups having 1 to 4 carbon atoms, cyclohexyl groups, phenyl groups, benzyl groups, α-chloromethyl groups, trimethylsiloxy groups, triethylsiloxy groups, and triphenylsiloxy groups. A methyl group or an ethyl group is preferred from the viewpoint of good curability of the polymer having a reactive silicon group and stability of the curable composition. An α-chloromethyl group is preferred from the viewpoint of a fast curing rate of the cured product. A methyl group is preferred from the viewpoint of being readily available.

[0050] In formula (2) above, Z represents a halogen atom, a hydroxyl group, or a hydrolyzable group. Z may be the same or different from each other. Examples of hydrolyzable groups include alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, sulfanyl groups, and alkenyloxy groups. Alkoxy groups are preferred because they are mildly hydrolyzable and easy to handle. Methoxy, ethoxy, and isopropoxy groups are preferred alkoxy groups, with methoxy or ethoxy groups being more preferred. When the alkoxy group is a methoxy or ethoxy group, siloxane bonds are quickly formed, making it easier to form a crosslinked structure in the cured product, which tends to result in good physical properties of the cured product.

[0051] In equation (2) above, a is an integer between 0 and 2. When a is 2, R 2 These can be the same or different from each other. When a is 0 or 1, Z can be the same or different from each other. Since the physical properties of the cured product tend to be excellent, a is preferably 0 or 1, and more preferably a is 1.

[0052] Examples of the reactive silicon group represented by formula (2) include trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, methyldiisopropoxysilyl group, (α-chloromethyl)dimethoxysilyl group, and (α-chloromethyl)diethoxysilyl group. From the viewpoint of high activity and good curability, trimethoxysilyl group, triethoxysilyl group, dimethoxymethylsilyl group, and diethoxymethylsilyl group are preferred, and dimethoxymethylsilyl group and trimethoxysilyl group are more preferred.

[0053] <Curable composition> The curable composition is obtained by mixing the reactive silicon group-containing organic polymer with other necessary components. The content of the reactive silicon group-containing organic polymer relative to the total mass of the curable composition is preferably 1 to 50% by mass, more preferably 1 to 45% by mass, and even more preferably 2 to 40% by mass. If the content is below the upper limit of the above range, the cured product will have better strength and better elongation properties.

[0054] [Other ingredients] Examples of the other components mentioned above include curable compounds other than reactive silicon group-containing organic polymers, curing catalysts (silanol condensation catalysts), fillers, plasticizers, thixotropic agents, stabilizers, adhesion modifiers, property modifiers, dehydrating agents, adhesion-improving resins, reinforcing materials such as fillers, surface modifiers, flame retardants, foaming agents, solvents, and silicates. Other components can be used in any combination without limitation from those conventionally known as described in International Publication No. 2013 / 180203, International Publication No. 2014 / 192842, International Publication No. 2016 / 002907, Japanese Patent Publication No. 2014-88481, Japanese Patent Publication No. 2015-10162, Japanese Patent Publication No. 2015-105293, Japanese Patent Publication No. 2017-039728, Japanese Patent Publication No. 2017-214541, etc. Two or more of each component may be used in combination.

[0055] [Mechanism of Action] In hydrosilylation reactions, the use of carboxylic acid compounds accelerates the reaction. However, if carboxylic acid compounds remain after the reaction, these compounds act as acid catalysts for de-alcoholization condensation reactions even during polymer storage, increasing the viscosity of the polymer and leading to reduced storage stability. In contrast, in this invention, by adding a halogenated silane compound during or after the hydrosilylation reaction, some or all of the carboxylic acid compound is converted to hydrogen halides, suppressing its action as an acid catalyst, and the generated hydrogen halides themselves are easily removed in post-reaction processing steps. As a result, it is presumed that both accelerated hydrosilylation and improved storage stability of the polymer can be achieved.

[0056] [Application] Suitable applications for the curable composition containing the reactive silicon group-containing organic polymer of the present invention include adhesives, sealants (e.g., elastic sealants for buildings, sealants for double-glazed windows, sealing materials for rust prevention and waterproofing of glass edges, back-surface sealing materials for solar cells, sealing materials for buildings, sealing materials for ships, sealing materials for automobiles, and sealing materials for roads), and electrical insulating materials (insulating coatings for electric wires and cables). In particular, it is suitable for adhesive applications where a high modulus, good tensile strength, and elongation properties of the cured product are required. [Examples]

[0057] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following description.

[0058] ≪Measurement Methods and Evaluation Methods≫ <Mn、Mw / Mn> Using an HLC-8220GPC (Tosoh Corporation product name), a TSKgel SupermultiporeHZ-M column (Tosoh Corporation product name), and tetrahydrofuran as the solvent, the sample pump was set to 0.350 mL / min, the reference pump to 0.350 mL / min, the detector temperature to 40°C, and the acquisition time to 6 to 15 minutes. Mw, Mn, and Mw / Mn were determined by analyzing the peaks that appeared between 6 and 11 minutes of acquisition.

[0059] <Hydroxyvalue of oxyalkylene polymers> The hydroxyl value (mgKOH / g) present in the oxyalkylene polymer was analyzed using the hydroxyl value measurement method in accordance with JIS K1557:2007.

[0060] <Method for measuring unsaturated value> The unsaturated value (hereinafter referred to as USV) of the polymer was determined according to the unsaturated value measurement method (Wijs method). Specifically, approximately 2 g of the polymer was placed in an Erlenmeyer flask, accurately weighed, and dissolved in 40 ml of chloroform. Wijs reagent was accurately weighed and added using a 20 ml volumetric pipette, and the flask was left in a cool, dark place for 1 hour. A potassium iodide aqueous solution (2 g of potassium iodide dissolved in 100 ml of water) with a few drops of starch solution added was added to the flask, and N / 10 sodium thiosulfate was added dropwise while stirring until the solution in the flask became colorless and transparent. The unsaturated value was determined from the endpoint using the following formula. For the blank titration, the above procedure was performed using chloroform without the addition of the polymer. Unsaturated value (mmol / g) = ((Blank titration volume (ml) - Sample titration volume (ml)) × Potency of sodium thiosulfate solution) ÷ (20 × Sample (g))

[0061] <Silylation rate> The silylation rate of the polymer is 1 Measurement was performed using the internal standard method of H-NMR. The number of terminal groups in the oxyalkylene polymers shown in Tables 1-3 is the hydroxyl group of the initiator. The number of reactive silicon groups introduced per molecule was calculated using the following formula. The number of reactive silicon groups per molecule 1 Measurement was performed using the internal standard method of H-NMR.

[0062] <Viscosity> A 1 mL sample of the polymer was taken, and its viscosity was measured using an E-type viscometer (Toki Sangyo Co., Ltd. product name: RE80) under rotor No. 4 conditions. JS14000 (Nippon Grease Co., Ltd. product name) was used as the calibration standard solution. The measurement temperature was 25 ± 2°C.

[0063] <Viscosity increase rate> The viscosity of each polymer was measured (hereinafter referred to as "initial viscosity"). Fifteen g of each polymer was transferred to a 24 mL glass bottle, the gas phase was replaced with nitrogen, the bottle was sealed, and it was left standing in a 90°C constant temperature bath. After two weeks, the polymer was removed from the constant temperature bath and left to stand at room temperature, and then its viscosity was measured (hereinafter referred to as "viscosity after accelerated testing"). The viscosity increase rate was calculated using the following formula and evaluated according to the following criteria. Viscosity increase rate (unit: %) = (Viscosity after accelerated testing - Initial viscosity) / (Initial viscosity) × 100 AA: The viscosity increase rate is 10% or less. A: The viscosity increase rate is greater than 10% but 15% or less. B: The viscosity increase rate is greater than 15% but less than or equal to 20%. C: Viscosity increase rate is greater than 20%.

[0064] <Evaluation of tensile properties (H-type test)> H-shaped test specimens were prepared in accordance with the test methods for building sealants specified in JIS A 1439:2016, and their tensile properties were evaluated. The curable composition to be measured was filled into a 2 mm thick mold and cured at 23°C and 50% humidity for 7 days, followed by curing at 50°C and 65% humidity for another 7 days. The resulting cured material was subjected to a tensile test using a Tensilon testing machine at a tensile speed of 500 mm / min, and the modulus (M50, unit: N / mm²) of the stress at 50% elongation was determined. 2 ), stress when stretched to 100% (M100, unit: N / mm 2 ), tensile strength (Tmax, unit: N / mm²), which is the maximum point cohesive force. 2 The maximum point elongation (Emax, in %) was measured. A higher value for M50 and M100 indicates a harder cured material; a higher value for maximum cohesive force indicates higher tensile strength; and a higher value for maximum elongation indicates better elongation.

[0065] Examples 1 to 32 and Example 42 are examples, and Examples 33 to 41 are comparative examples.

[0066] (Example 1: Conversion A1) Using polyoxypropylene glycol as an initiator and a zinc hexacyanocobaltate complex with t-butyl alcohol as a ligand (hereinafter also referred to as "TBA-DMC catalyst") as a catalyst, propylene oxide was polymerized to obtain a hydroxyl-containing oxyalkylene polymer (precursor polymer P1) with two hydroxyl groups at its ends. The hydroxyl value of the obtained precursor polymer P1 was 6.2 mgKOH / g. 1.05 molar equivalents of sodium methoxide were added to the hydroxyl groups of precursor polymer P1, and methanol was removed by distillation under reduced pressure. An excess amount of allyl chloride was added to the hydroxyl groups of precursor polymer P1 and the reaction was carried out, and unreacted allyl chloride was removed under reduced pressure. The mixture was purified to remove the metal salts, and an unsaturated group-containing oxyalkylene polymer (precursor polymer Q1) was obtained by converting the hydroxyl groups to allyloxy groups. The USV of the obtained precursor polymer Q1 was 0.12 mmol / g. A solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (hereinafter referred to as "Karstedt catalyst"), which is a platinum catalyst, in isopropyl alcohol (platinum concentration 3 wt%) (212.3 ml per 1000 g of precursor polymer Q1, with platinum added at a rate of 6.4 ppm by mass relative to precursor polymer Q1) and a carboxylic acid compound (0.38 g per 1000 g of precursor polymer Q1, with 5 mol per 1 mol of unsaturated groups in precursor polymer Q1) is mixed with acetic acid. Furthermore, a solution of chlorotrimethylsilane, a halogenated silane compound, dissolved in acetonitrile at a molar ratio of 1.2 relative to the carboxylic acid compound (a solution containing acetic acid and chlorotrimethylsilane) was added to precursor polymer Q1. To 1 mole of unsaturated groups of the precursor polymer Q1, 1.1 moles of dimethoxymethylsilane were added as a silylation agent, and the mixture was reacted at 70°C for 3 hours. Unreacted silylation agents and other residues were then removed under reduced pressure at 80°C for 2 hours to obtain polymer A1. Table 1 shows the number of terminal groups per molecule, the number of reactive silicon groups introduced per molecule, Mn, Mw / Mn, silylation rate, and viscosity increase rate of the obtained polymer A1 (similarly shown in Tables 1-3 below).

[0067] (Example 2: Polymer A2) In Example 1, the platinum catalyst was replaced with hexachloroplatin(IV) acid hexahydrate (13.3 mg per 1000 g of precursor polymer Q1, or 5.0 ppm by mass of platinum relative to precursor polymer Q1). Otherwise, the same procedure as in Example 1 was carried out to obtain polymer A2.

[0068] (Example 3: Polymer A3) In Example 1, the carboxylic acid compound was replaced with formic acid. Otherwise, the same procedure as in Example 1 was performed to obtain polymer A3.

[0069] (Example 4: Polymer A4) In Example 1, the carboxylic acid compound was replaced with trifluoroacetic acid. Otherwise, the same procedure as in Example 1 was carried out to obtain polymer A4.

[0070] (Example 5: Polymer A5) In Example 1, the carboxylic acid compound was replaced with benzoic acid. Otherwise, the same procedure as in Example 1 was performed to obtain polymer A5.

[0071] (Example 6: Polymer A6) In Example 1, the carboxylic acid compound was replaced with crotonic acid. Otherwise, the same procedure as in Example 1 was performed to obtain polymer A6.

[0072] (Example 7: Polymer A7) In Example 1, the carboxylic acid compound was replaced with phenylpropiolic acid. Otherwise, the same procedure as in Example 1 was carried out to obtain polymer A7.

[0073] (Example 8: Polymer A8) In Example 1, the halogenated silane compound was replaced with bromotrimethylsilane. Otherwise, the same procedure as in Example 1 was followed to obtain polymer A8.

[0074] (Example 9: Polymer A9) In Example 1, the halogenated silane compound was replaced with chlorotriisopropylsilane. Otherwise, the same procedure as in Example 1 was carried out to obtain polymer A9.

[0075] (Example 10: Polymer A10) In Example 1, the halogenated silane compound was replaced with chloroethyldimethylsilane. Otherwise, the same procedure as in Example 1 was carried out to obtain polymer A10.

[0076] (Example 11: diverA11) In Example 1, the halogenated silane compound was replaced with dimethyl-n-octylchlorosilane. Otherwise, the same procedure as in Example 1 was carried out to obtain polymer A11.

[0077] (Example 12: diffusionA12) In Example 1, the halogenated silane compound was replaced with chloro(dodecyl)dimethylsilane. Otherwise, the same procedure as in Example 1 was carried out to obtain polymer A12.

[0078] (Example 13: Polymer A13) In Example 1, the halogenated silane compound was replaced with chlorodimethylisopropylsilane. Otherwise, the same procedure as in Example 1 was carried out to obtain polymer A13.

[0079] (Example 14: Polymer A14) In Example 1, the halogenated silane compound was replaced with chlorodimethylphenylsilane. Otherwise, the same procedure as in Example 1 was performed to obtain polymer A14.

[0080] (Example 15: Polymerization A15) In Example 1, the halogenated silane compound was replaced with chlorodimethylvinylsilane. Otherwise, the same procedure as in Example 1 was carried out to obtain polymer A15.

[0081] (Example 16: Shift A16) In Example 1, the silylation agent was changed to trimethoxysilane. Otherwise, the same procedure as in Example 1 was performed to obtain polymer A16.

[0082] (Example 17: fluxA17) In Example 1, the amount of carboxylic acid compound used was changed to 0.9 mol% per 1 mol of unsaturated groups in the precursor polymer Q1. Otherwise, the same procedure as in Example 1 was performed to obtain polymer A17.

[0083] (Example 18: Polymer A18) In Example 1, the amount of carboxylic acid compound used was changed to 1.0 mol% per 1 mol of unsaturated groups in the precursor polymer Q1. Otherwise, the same procedure as in Example 1 was carried out to obtain polymer A18.

[0084] (Example 19: Polymer A19) In Example 1, the amount of carboxylic acid compound used was changed to 10 mol% per 1 mol of unsaturated groups in the precursor polymer Q1. Otherwise, the same procedure as in Example 1 was carried out to obtain polymer A19.

[0085] (Example 20: Polymer A20) In Example 1, the amount of carboxylic acid compound used was changed to 11 mol% per 1 mol of unsaturated groups in the precursor polymer Q1. Otherwise, the same procedure as in Example 1 was carried out to obtain polymer A20.

[0086] (Example 21: fluxA21) In Example 1, the molar ratio of the silane halide compound to the carboxylic acid compound was changed to 0.45. Otherwise, the same procedure as in Example 1 was performed to obtain polymer A21. The amount of the carboxylic acid compound was the same as in Example 1, and the amount of the silane halide compound was changed. The same procedure was followed for Examples 22 to 26.

[0087] (Example 22: WaveA22) In Example 1, the molar ratio of the halogenated silane compound to the carboxylic acid compound was changed to 0.5. Otherwise, the same procedure as in Example 1 was performed to obtain polymer A22.

[0088] (Example 23: Polymer A23) In Example 1, the molar ratio of the halogenated silane compound to the carboxylic acid compound was changed to 1. Otherwise, the same procedure as in Example 1 was performed to obtain polymer A23.

[0089] (Example 24: Polymer A24) In Example 1, the molar ratio of the halogenated silane compound to the carboxylic acid compound was changed to 1.5. Otherwise, the same procedure as in Example 1 was performed to obtain polymer A24.

[0090] (Example 25: polymerizationA25) In Example 1, the molar ratio of the halogenated silane compound to the carboxylic acid compound was changed to 2. Otherwise, the same procedure as in Example 1 was performed to obtain polymer A25.

[0091] (Example 26: amplificationA26) In Example 1, the molar ratio of the halogenated silane compound to the carboxylic acid compound was changed to 2.2. Otherwise, the same procedure as in Example 1 was performed to obtain polymer A26.

[0092] (Example 27: Polymer A27) Instead of using the precursor polymer P1 in Example 1, the same procedure as in Example 1 was performed to obtain a hydroxyl group-containing oxyalkylene polymer (precursor polymer P2) with a different degree of polymerization from precursor polymer P1, in which two terminal groups are hydroxyl groups. The hydroxyl value of the obtained precursor polymer P2 was 7.5 mg KOH / g. To the hydroxyl groups of precursor polymer P2, 1.15 molar equivalents of sodium methoxide were added, and methanol was removed under reduced pressure. Next, 1.05 molar equivalents of allyl glycidyl ether were added to the hydroxyl groups of precursor polymer P2, and the mixture was reacted at 130°C for 2 hours. Furthermore, 0.28 molar equivalents of sodium methoxide were added to the hydroxyl groups of precursor polymer P2, and methanol was removed. Then, 2.10 molar equivalents of allyl chloride were added to the hydroxyl groups of precursor polymer P2, and the mixture was reacted at 130°C for 2 hours, and unreacted allyl chloride was removed under reduced pressure. After purification to remove metal salts, an unsaturated group-containing oxyalkylene polymer (precursor polymer Q2) with 2.0 allyl groups per terminal group was obtained. The USV of the obtained precursor polymer Q2 was 0.29 mmol / g. An isopropyl alcohol solution of Karstedt catalyst (platinum concentration 3 wt%) (212.3 ml per 1000 g of precursor polymer Q2, with platinum added at a rate of 6.4 ppm by mass relative to precursor polymer Q2) and acetic acid, a carboxylic acid compound (0.76 g per 1000 g of precursor polymer Q2, with 5 mol per 1 mol of unsaturated groups in precursor polymer Q2), were mixed. Furthermore, a solution of chlorotrimethylsilane, a halogenated silane compound, dissolved in acetonitrile at a molar ratio of 1.2 relative to the carboxylic acid compound was added to the precursor polymer Q2. 1.1 mol of dimethoxymethylsilane was added per 1 mol of unsaturated groups in precursor polymer Q2, and the reaction was carried out at 70°C for 5 hours. Unreacted silylates and other components were removed under reduced pressure at 80°C for 2 hours to obtain polymer A27.

[0093] (Example 28: A28) 1.05 molar equivalents of sodium methoxide were added to the hydroxyl groups of precursor polymer P2, and methanol was removed under reduced pressure. Next, an excess amount of propargyl bromide was reacted with the hydroxyl groups of precursor polymer P1 to obtain an oxyalkylene polymer (precursor polymer Q3) having 1.0 propargyl group per terminal group. The USV of the obtained precursor polymer Q3 was 0.29 mmol / g. An isopropyl alcohol solution of Karstedt catalyst (platinum concentration 3 wt%) (212.3 ml per 1000 g of precursor polymer Q3, equivalent to 6.4 ppm by mass of platinum relative to precursor polymer Q3) and acetic acid, a carboxylic acid compound (0.76 g per 1000 g of precursor polymer Q3, equivalent to 5 mol per 1 mol of unsaturated groups in precursor polymer Q3), were mixed. Furthermore, a solution of chlorotrimethylsilane, a halogenated silane compound, dissolved in acetonitrile at a molar ratio of 1.2 relative to the carboxylic acid compound was added to precursor polymer Q3. 4.0 mol of dimethoxymethylsilane was added per 1 mol of propargyl groups in precursor polymer Q3, and the reaction was carried out at 70°C for 3 hours. Unreacted silylates and other components were removed under reduced pressure at 80°C for 2 hours to obtain polymer A28.

[0094] (Example 29: polymerizationA29) 8.39 g of cuprous bromide and 112 mL of acetonitrile were added to a 2 L flask and heated and stirred at 70°C under a nitrogen stream for 20 minutes. 17.6 g of diethyl 2,5-dibromoadipate, 130 mL of ethyl acrylate, 720 mL of butyl acrylate, and 251 g of stearyl acrylate were added, and the mixture was heated and stirred at 70°C for another 40 minutes. 0.41 mL of pentamethyldiethylenetriamine (hereinafter also referred to as "triamine") was added to initiate the reaction. Heating and stirring continued at 70°C, and an additional 2.05 mL of triamine was added. 330 minutes after the start of the reaction, 244 mL of 1,7-octadiene and 4.1 mL of triamine were added, and heating and stirring continued at 70°C. Heating was stopped 570 minutes after the start of the reaction. The resulting reaction solution was diluted with toluene and filtered. The filtrate was subjected to reduced-pressure heat treatment to obtain an unpurified acrylic ester polymer having alkenyl groups at the end. The unpurified acrylic acid ester polymer had 2.0 alkenyl groups per molecule. Furthermore, under a nitrogen atmosphere, the entire amount of the unpurified acrylic ester polymer, 17.2 g of potassium acetate, and 700 mL of N,N-dimethylacetamidomethyl (hereinafter referred to as "DMAc") were added to a 2 L flask and heated and stirred at 100°C for 10 hours. The reaction solution was heated under reduced pressure to remove the DMAc, and toluene was added and the mixture was filtered. The filtrate was heated under reduced pressure to remove volatile components, and the remainder was added to a 2 L flask. 100 g of adsorbent (a mixture of Kyoward 500SN and Kyoward 700SN (both product names of Kyowa Chemical Industry Co., Ltd.) in a 1:1 mass ratio) was added and the mixture was heated and stirred at 130°C under a nitrogen stream for 9 hours. The mixture was diluted with toluene, filtered to remove the adsorbent, and toluene in the filtrate was removed under reduced pressure to obtain an unsaturated group-containing acrylic ester polymer (precursor polymer Q4). A solution of Karstedt catalyst in isopropyl alcohol (platinum concentration 3 wt%) (212.3 ml per 1000 g of precursor polymer Q4, equivalent to 6.4 ppm by mass of platinum relative to precursor polymer Q4) and a carboxylic acid compound (0.38 g per 1000 g of precursor polymer Q4, equivalent to 5 mol per 1 mol of unsaturated groups of precursor polymer Q4) acetic acid were mixed. Furthermore, a solution of chlorotrimethylsilane, a halogenated silane compound, dissolved in acetonitrile at a molar ratio of 1.2 to the carboxylic acid compound was added to the precursor polymer Q4. For every 1 mol of unsaturated groups of precursor polymer Q4, 1.1 mol of trimethoxysilane was added as a silylation agent. The reaction was carried out at 70°C for 3 hours, and then unreacted silylation agents and other residues were removed under reduced pressure at 80°C for 2 hours to obtain polymer A29.

[0095] (Example 30: Polymer A30) In Example 1, the initiator was changed to n-butyl alcohol, and the same procedure as in Example 1 was performed to obtain a hydroxyl group-containing oxyalkylene polymer (precursor polymer P3) with one terminal group being a hydroxyl group, an unsaturated group-containing oxyalkylene polymer (precursor polymer Q5), and polymer A30, which is a reactive silicon group-containing oxyalkylene polymer. The hydroxyl value of the obtained precursor polymer P3 was 11.2 mgKOH / g, and the USV of precursor polymer Q5 was 0.22 mmol / g.

[0096] (Example 31: Polymer A31) In Example 1, the initiator was changed to glycerin, and the same procedure as in Example 1 was performed to obtain a hydroxyl group-containing oxyalkylene polymer (precursor polymer P4) with three hydroxyl groups at its terminal, an unsaturated group-containing oxyalkylene polymer (precursor polymer Q6), and polymer A31, a reactive silicon group-containing oxyalkylene polymer. The hydroxyl value of the obtained precursor polymer P4 was 7.0 mgKOH / g, and the USV of precursor polymer Q6 was 0.14 mmol / g.

[0097] (Example 32: Polymer A32) In Example 1, the initiator was changed to sorbitol, and the same procedure as in Example 1 was performed to obtain a hydroxyl group-containing oxyalkylene polymer (precursor polymer P5) with six terminal groups being hydroxyl groups, an unsaturated group-containing oxyalkylene polymer (precursor polymer Q7), and polymer A32, a reactive silicon group-containing oxyalkylene polymer. The hydroxyl value of the obtained precursor polymer P5 was 8.0 mgKOH / g, and the USV of precursor polymer Q7 was 0.16 mmol / g.

[0098] (Example 33: Polymer A33) In Example 1, instead of using carboxylic acid compounds and halogenated silane compounds, a solution of platinum catalyst dissolved in acetonitrile was added. Otherwise, the same procedure as in Example 1 was carried out to obtain polymer A33.

[0099] (Example 34: Polymer A34) In Example 1, instead of using a halogenated silane compound, a platinum catalyst and a carboxylic acid compound were dissolved in acetonitrile and the solution was added. Otherwise, the same procedure as in Example 1 was carried out to obtain polymer A34.

[0100] (Example 35: Polymer A35) In Example 27, instead of using a halogenated silane compound, the platinum catalyst and carboxylic acid compound were dissolved in acetonitrile and the solution was added. Otherwise, the same procedure as in Example 27 was carried out to obtain polymer A35.

[0101] (Example 36: Polymer A36) In Example 28, instead of using a halogenated silane compound, the platinum catalyst and carboxylic acid compound were dissolved in acetonitrile and the solution was added. Otherwise, the same procedure as in Example 28 was carried out to obtain polymer A36.

[0102] (Example 37: Polymer A37) In Example 29, instead of using a halogenated silane compound, the platinum catalyst and carboxylic acid compound were dissolved in acetonitrile and the solution was added. Otherwise, the same procedure as in Example 29 was followed to obtain polymer A37.

[0103] (Example 38: Polymer A38) In Example 30, instead of using a halogenated silane compound, the platinum catalyst and carboxylic acid compound were dissolved in acetonitrile and the solution was added. Otherwise, the same procedure as in Example 30 was carried out to obtain polymer A38.

[0104] (Example 39: Polymer A39) In Example 31, instead of using a halogenated silane compound, the platinum catalyst and carboxylic acid compound were dissolved in acetonitrile and the solution was added. Otherwise, the same procedure as in Example 31 was carried out to obtain polymer A39.

[0105] (Example 40: Polymer A40) In Example 32, instead of using a halogenated silane compound, the platinum catalyst and carboxylic acid compound were dissolved in acetonitrile and the solution was added. Otherwise, the same procedure as in Example 32 was carried out to obtain polymer A40.

[0106] (Example 41: Polymer A41) In Example 1, instead of using a carboxylic acid compound, a platinum catalyst and a halogenated silane compound were dissolved in acetonitrile and the solution was added. The amount of halogenated silane compound added was the same as in Example 1. Otherwise, the same procedure as in Example 1 was performed to obtain polymer A41.

[0107] (Example 42: Polymer A42) In Example 1, a silylation reaction was carried out using the obtained precursor polymer Q1. An isopropyl alcohol solution of Karstedt catalyst (platinum concentration 3 wt%) (212.3 ml per 1000 g of precursor polymer Q1, with platinum added at a ratio of 6.4 ppm by mass relative to precursor polymer Q1) and acetic acid, a carboxylic acid compound (0.38 g per 1000 g of precursor polymer Q1, or 5 mol per 1 mol of unsaturated groups of precursor polymer Q1), were mixed and dissolved in acetonitrile. This solution was then added to precursor polymer Q1. 1.1 mol of dimethoxymethylsilane was added as a silylation agent per 1 mol of unsaturated groups of precursor polymer Q1, and the reaction was carried out at 70°C for 3 hours. Then, chlorotrimethylsilane, a halogenated silane compound, was added at a molar ratio of 1.2 relative to the carboxylic acid compound, and unreacted silylation agents were removed under reduced pressure at 80°C for 2 hours to obtain polymer A42.

[0108] [Table 1]

[0109] [Table 2]

[0110] [Table 3]

[0111] Examples 1 to 32 describe a manufacturing method according to the first embodiment of the present invention, and Example 42 describes a manufacturing method according to the second embodiment of the present invention. In the examples where hydrosilylation was carried out by adding a Group 8 metal catalyst and a carboxylic acid compound (Examples 1 to 32, 34 to 40, and 42), the silylation rate was higher and the hydrosilylation reaction was accelerated compared to the examples where hydrosilylation was carried out with only a Group 8 metal catalyst (Examples 33 and 41). Furthermore, compared to the case where hydrosilylation was carried out without adding a halogenated silane compound, as in Examples 33 to 40, adding a halogenated silane compound to the hydrosilylation reaction, as in Examples 1 to 32 and 41, suppressed the increase in viscosity of the polymer and improved storage stability. In other words, as shown in Examples 1 to 32, which are manufacturing methods according to the first embodiment of the present invention, by adding a co-catalyst A containing an eighth metal catalyst, a carboxylic acid compound, and a halogenated silane compound, it was possible to achieve both acceleration of the hydrosilylation reaction and suppression of the viscosity increase rate of the polymer, thereby improving storage stability. Furthermore, as shown in Example 42, which is a manufacturing method according to the second embodiment of the present invention, by adding a co-catalyst B containing an eighth metal catalyst and a carboxylic acid compound but not a halogenated silane compound to carry out the hydrosilylation reaction, and then adding a halogenated silane compound after the reaction is complete, it was also possible to achieve both acceleration of the hydrosilylation reaction and suppression of the viscosity increase rate of the polymer, thereby improving storage stability.

[0112] <Other ingredients> The additives listed in Tables 4 and 5 are as follows: White gloss CCR: Collagenous calcium carbonate, product name of Shiraishi Kogyo Co., Ltd. Whiteon SB: Heavy calcium carbonate, product name of Shiraishi Kogyo Co., Ltd. R820: Titanium dioxide, product name of Ishihara Sangyo Co., Ltd. DINP: Sanso-sizer DINP, diisononyl phthalate, product name of Shin-Nippon Rika Co., Ltd. DIDP: Diisodecyl phthalate, manufactured by Mitsubishi Chemical Corporation. PMLS4012: Preminol S4012, a high molecular weight polyol with two hydroxyl groups per molecule and a manganese content of 13,000, is a product name of AGC Corporation. Sansoizer EPS: 4,5-Epoxycyclohexane-1,2-dicarboxylate-di-2-ethylhexyl, product name of Shin Nippon Rika Co., Ltd. Disparon 6500: Hydrogenated castor oil-based thixotropic agent, product name of Kusumoto Chemical Co., Ltd. Disparon 305: Hydrogenated castor oil-based thixotropic agent, product name of Kusumoto Chemical Co., Ltd. Balloon 80GCA: Organic balloon, product name of Matsumoto Oil & Fat Co., Ltd. M309: Arronix M-309: Photocurable resin, product name of Toagosei Co., Ltd. Glycerin monostearate: Reagent, manufactured by Tokyo Chemical Industry Co., Ltd. KBM-1003: Vinyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd. A-171: Vinyltrimethoxysilane, Momentive product name. KBM-403:3-Glycidyloxypropyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd. KBM-603: 3-(2-aminoethylamino)propyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd. A-1120: 3-(N-2-aminoethylamino)propyltrimethoxysilane, Momentive product name. TINUVIN765: A tertiary amine-containing hindered amine-based light stabilizer; BASF product name. TINUVIN770: A tertiary amine-containing hindered amine-based light stabilizer; BASF product name. Sanol LS770: Hindered amine-based light stabilizer, product name of Sankyo Life Tech Co., Ltd. IRGANOX1010: Hindered phenol antioxidant, BASF product name. TINUVIN326: A benzotriazole-based UV absorber, a product name of BASF. TINUVIN327: A benzotriazole-based UV absorber, a product name of BASF. Tung oil: Air oxidation curing compound, manufactured by Kimura Company. DBTDL: Dibutyltin dilaurate. U-220H: Dibutyltin bis(acetyl acetate), product name of Nitto Kasei Co., Ltd. Stanoct: Stannous octylate, product name of Yoshitomi Pharmaceutical Co., Ltd. Laurylamine: Reagent, manufactured by Junsei Chemical Co., Ltd. Glomax LL: Calcined kaolin, product name of Takehara Chemical Industry Co., Ltd.

[0113] Preparation of curable compositions A curable composition was prepared by adding polymers in the amounts (parts by mass) shown in Tables 6 and 7 and additives in the amounts (parts by mass) shown in Tables 4 and 5. The amounts of each component shown in Tables 4 and 5 are relative to 100 parts by mass of the total polymer (unit: parts by mass). The resulting curable composition was used to evaluate its tensile properties (H-type test). The results are shown in Tables 6 and 7.

[0114] [Table 4]

[0115] [Table 5]

[0116] [Table 6]

[0117] [Table 7]

Claims

1. A method for producing a reactive silicon group-containing organic polymer represented by the following formula (2), comprising adding a co-catalyst A containing a group 8 metal catalyst and a carboxylic acid compound and a halogenated silane compound represented by the following formula (1) to react an unsaturated group-containing organic polymer with a silylating agent, or adding a co-catalyst B containing the group 8 metal catalyst and a carboxylic acid compound but not the halogenated silane compound to react an unsaturated group-containing organic polymer with a silylating agent, and then adding the halogenated silane compound, wherein The carboxylic acid compound has 1 to 10 carbon atoms. The amount of carboxylic acid compound used in co-catalysts A and B is 0.1 to 20 mol% relative to 1 mol of unsaturated groups in the unsaturated group-containing organic polymer. In the co-catalyst A, the carboxylic acid compound and the halogenated silane compound are mixed in a molar ratio of 0.5 to 2.

0. A method for producing a reactive silicon group-containing organic polymer, wherein the molar ratio of the halogenated silane compound to the carboxylic acid compound contained in the co-catalyst B is 0.5 to 2.

0. X ｍ SiR １ ４－ｍ Equation (1) -SiR ２ ａ Z ３－ａ Equation (2) [In formula (1), X is a halogen atom, m is an integer from 1 to 3, and R １ represents a monovalent organic group having 1 to 20 carbon atoms and is an organic group other than a hydrolyzable group. When m is 1 or 2, R １ may be the same as or different from each other. When m is 2 or 3, X may be the same as or different from each other. In formula (2), R ２ represents a monovalent organic group having 1 to 20 carbon atoms and is an organic group other than a hydrolyzable group, Z represents a halogen atom, a hydroxyl group, or a hydrolyzable group. a is an integer from 0 to 2. When a is 2, R ２ may be the same as or different from each other, and when a is 0 or 1, Z may be the same as or different from each other.]

2. A method for producing a reactive silicon group-containing organic polymer according to claim 1, wherein the Group 8 metal catalyst comprises at least one metal selected from the group consisting of cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum.

3. A method for producing a reactive silicon group-containing organic polymer according to claim 1 or 2, wherein the halogenated silane compound is chlorotrimethylsilane.

4. A method for producing a reactive silicon group-containing organic polymer according to claim 1 or 2, wherein the reactive silicon group-containing organic polymer is a polymer having units based on oxyalkylene monomers.

5. The method for producing a reactive silicon group-containing organic polymer according to claim 3, wherein the reactive silicon group-containing organic polymer is a polymer having units based on oxyalkylene monomers.

6. A method for producing a reactive silicon group-containing organic polymer according to claim 1 or 2, wherein the reactive silicon group-containing organic polymer is a polymer having units based on an alkyl acrylate monomer or an alkyl methacrylate monomer.

7. The method for producing a reactive silicon group-containing organic polymer according to claim 3, wherein the reactive silicon group-containing organic polymer is a polymer having units based on an alkyl acrylate monomer or an alkyl methacrylate monomer.

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