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• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/06—Preparatory processes
  • C08G77/08—Preparatory processes characterised by the catalysts used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2282—Unsaturated compounds used as ligands
  • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
  • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
  • C07F15/0046—Ruthenium compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
  • B01J2231/32—Addition reactions to C=C or C-C triple bonds
  • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/82—Metals of the platinum group
  • B01J2531/821—Ruthenium

Definitions

• the present invention relates to a ruthenium complex, a method for producing a silyl group-containing compound, a silyl group-containing polymer mixture, a curable composition, and a cured product.
• Organic polymers containing silicon atoms particularly organic polymers containing silyl groups (hereinafter referred to as "hydrolyzable silyl groups”) that have hydroxyl groups or hydrolyzable groups on the silicon atoms and can form siloxane bonds, are known as moisture-reactive polymers. These harden through a hydrolysis reaction to form flexible rubber-like hardened products, and are therefore used in many industrial products such as sealants, adhesives, coating materials, paints, and pressure sensitive adhesives.
• a commonly known method for obtaining such silyl group-containing organic polymers is to subject an allyl group-containing organic polymer to a hydrosilane compound to a hydrosilylation reaction in the presence of a metal catalyst.
• a common problem with hydrosilylation of allyl group-containing compounds using a metal catalyst is that side reactions such as isomerization to 1-propenyl groups (internal olefins) and hydrogenation occur during the reaction.
• the Karstedt catalyst platinum divinyldisiloxane complex
• the above-mentioned side reactions proceed at about 20%, limiting the introduction rate of silyl groups.
• the rubber-like cured product obtained by curing the curable composition containing the hydrolyzable silyl group-containing organic polymer has room for improvement in its modulus, tensile strength, etc.
• Patent Document 1 reports that the corresponding silylated product can be efficiently produced by reacting an allyl ether compound with a hydrosilane compound in the presence of a specific ruthenium complex.
• the side reaction rate increases and the selectivity of the silylated product decreases, so the production of silylated products is limited to those with a molecular weight of 3,000 or less.
• the present invention aims to provide a ruthenium complex that can efficiently introduce a silyl group into an allyl group-containing compound in a hydrosilylation reaction, regardless of the molecular weight of the allyl group-containing compound, and a method for producing the silyl group-containing compound.
• a silylated product can be efficiently produced regardless of the molecular weight of the allyl group-containing compound. Furthermore, they have found that a method of adding a specific compound in advance when carrying out a hydrosilylation reaction of an allyl group-containing compound using a known ruthenium catalyst also allows for efficient production of a silylated product regardless of the molecular weight of the allyl group-containing compound, thus arriving at the present invention.
• the present invention relates to 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 an electron-withdrawing group is bonded to at least one or more of the carbon atoms forming the carbon-carbon double bond.
• the present invention also relates to a hydrosilylation reaction catalyst containing the above ruthenium complex (A).
• the present invention further relates to a method for producing a silyl group-containing compound (E), which comprises a step of mixing an allyl group-containing compound (C), a hydrosilane compound (D), and the hydrosilylation reaction catalyst to carry out a hydrosilylation reaction.
• the present invention also relates to a method for producing a silyl group-containing compound (E), which comprises a step of mixing an allyl group-containing compound (C), a hydrosilane compound (D), a ruthenium compound (A') that does not have compound (B) as a ligand, and compound (B) to carry out a hydrosilylation reaction, in which compound (B) has at least one carbon-carbon double bond in one molecule and has an electron-withdrawing group bonded to at least one or more of the carbon atoms forming the carbon-carbon double bond.
• the present invention also relates to a polymer mixture containing a hydrolyzable silyl group-containing polymer and the ruthenium complex (A); a curable composition containing the polymer mixture and a curing catalyst; and a cured product obtained by curing the curable composition.
• a ruthenium complex capable of efficiently introducing a silyl group into an allyl group-containing compound, regardless of the molecular weight of the allyl group-containing compound, by using the complex as a catalyst during the hydrosilylation reaction between an allyl group-containing compound and a hydrosilane compound, and a hydrosilylation reaction catalyst containing the ruthenium complex.
• a method for producing a silyl group-containing compound capable of highly efficiently introducing a silyl group into the hydrosilylation reaction between an allyl group-containing compound and a hydrosilane compound.
• a ruthenium complex (A) according to one embodiment of the present invention has a compound (B) as a ligand, and is characterized in that 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 it.
• such a ruthenium complex (A) exhibits high selectivity when used as a catalyst for the hydrosilylation reaction of an allyl group-containing compound with a hydrosilane compound, suppresses the by-production of a 1-propenyl group or a hydrogenated product (propyl group), and can efficiently produce a corresponding silylated product even if the silylated product is a high molecular weight product having a number average molecular weight of more than 3,000.
• the "ruthenium complex (A)" and the "compound (B)” will be described in detail.
• the ruthenium complex (A) is a ruthenium complex having a compound (B) as a ligand.
• the specific type of the ruthenium complex (A) is not particularly limited, except that the ruthenium complex (A) has a compound (B) as a ligand.
• the type of the compound (B) that the ruthenium complex (A) has as a ligand may be one type or two or more types.
• Ruthenium complex (A) can be produced by a method similar to a known production method.
• raw materials for ruthenium complex (A) include anhydrides and hydrates of compounds selected from ruthenium chloride (III), ruthenium bromide (III), and ruthenium iodide (III).
• a specific production method for ruthenium complex (A) is, for example, adding compound (B) to an ethanol solution of ruthenium chloride (III) hydrate, heating under reflux, filtering, and then drying.
• ruthenium chloride (III) hydrate When ruthenium chloride (III) hydrate is used as a raw material, heating under reflux may be performed in the presence of a basic compound such as sodium carbonate or sodium bicarbonate in order to neutralize hydrogen chloride generated during heating under reflux.
• a basic compound such as sodium carbonate or sodium bicarbonate
• the ruthenium complex (A) may have, as a ligand, a compound (B) as well as a compound (B') that does not fall under the category of compound (B).
• Compound (B') is a compound that can be coordinated to the ruthenium complex (A) and does not fall under the category of compound (B).
• Compound (B') that can be a ligand is not particularly limited, but examples thereof include 2,5-norbornadiene ligand, 1,5-cyclooctadiene ligand, p-cymene ligand, mesitylene ligand, benzene ligand, carbonyl ligand, isocyanide ligand, and arene ligand.
• ruthenium complex (A) has both compound (B) and compound (B') as ligands
• the proportion of compound (B) in the total ligands of ruthenium complex (A) is higher, since this can provide better selectivity.
• the proportion of compound (B) in the total ligands is preferably 1 to 100 mol%, more preferably 50 to 100 mol%, even more preferably 70 to 100 mol%, and even more preferably 90 to 100 mol%.
• Ruthenium complex (A) having compound (B) as a ligand can also be obtained by adding compound (B) to a system containing ruthenium compound (A') that does not have compound (B) as a ligand, and converting ruthenium compound (A') into ruthenium complex (A), using the method described below.
• Compound (B) is a compound capable of coordinating to a ruthenium complex.
• 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 it.
• Examples of the basic skeleton containing the carbon-carbon double bond in compound (B) include a norbornadiene skeleton, a cyclooctadiene skeleton, a benzene ring skeleton, a benzoquinone skeleton, and the like, and more specifically, a 2,5-norbornadiene skeleton, a 1,5-cyclooctadiene skeleton, a p-cymene skeleton, a mesitylene skeleton, a benzene ring skeleton, a benzoquinone skeleton, and the like.
• a norbornadiene skeleton or a benzene ring skeleton is preferable.
• the electron-withdrawing group examples include halogeno groups such as a fluoro group, a chloro group, a bromo group, and an iodo group, a cyano group, an aldehyde group, a nitro group, etc.
• the electron-withdrawing groups may be different in type.
• Compound (B) may have one or more electron-withdrawing groups in one molecule, but it preferably has two or more, more preferably has two to four, and particularly preferably has two or three.
• the type of electron-withdrawing group is preferably a halogeno group, more preferably a fluoro group, a bromo group or an iodine group, even more preferably a bromo group or an iodine group, and particularly preferably a bromo group.
• compound (B) preferably has one or more electron-withdrawing groups selected from a fluoro group, a bromo group and an iodine group in one molecule, more preferably has two or more.Furthermore, compound (B) preferably has one or more electron-withdrawing groups selected from a bromo group and an iodine group in one molecule.At this time, in addition to a bromo group and/or an iodine group, a fluoro group may be further included.
• These electron-withdrawing groups are preferably directly bonded to the carbon atoms forming the carbon-carbon double bond of compound (B).
• these electron-withdrawing groups are preferably directly bonded to the benzene ring.
• the structure of compound (B) consists of the above-mentioned basic skeleton combined with an electron-withdrawing group.
• the specific type of compound (B) is not particularly limited, and examples thereof include 2-bromonorbornadiene, 2,3-dibromonorbornadiene, 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
• compound (B) is preferably 2,3-dibromonorbornadiene, 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,3,5-tribromobenzene, 1,4-diiodobenzene, or hexabromobenzene, and is particularly preferably 2,3-dibromonorbornadiene, 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene, or 1,3,5-tribromobenzene. Only one type of compound (B) may be used, or two or more types may be used in combination.
• the method for producing a silyl group-containing compound (E) includes a step of subjecting an allyl group-containing compound (C) and a hydrosilane compound (D) to a hydrosilylation reaction in the presence of a ruthenium complex (A) as a hydrosilylation reaction catalyst.
• the ruthenium complex (A) is as described above.
• silyl group-containing compound (E) The specific structure of the silyl group-containing compound (E) according to the present embodiment is not particularly limited as long as it is a compound in which a propylene group derived from an allyl group-containing compound (C) is bonded to a silicon atom derived from a hydrosilane compound (D).
• the silyl group-containing compound (E) has a silyl group represented by the following general formula (1). -SiR a X b formula (1)
• R in general formula (1) represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.
• the hydrocarbon group may be saturated or unsaturated, and may be aliphatic, alicyclic, or aromatic.
• the hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms.
• the substituent is not particularly limited, and examples thereof include halogeno groups such as a chloro group, alkoxy groups such as a methoxy group, and amino groups such as an N,N-diethylamino group.
• R includes, for example, 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, toluyl, and 1-naphthyl; and aralkyl groups such as benzyl.
• alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, 2-ethylhex
• substituted or unsubstituted alkyl groups more preferably methyl, ethyl, chloromethyl, and methoxymethyl groups, even more preferably methyl and methoxymethyl groups, and particularly preferably methyl.
• R 1 substituted or unsubstituted alkyl groups
• X in the general formula (1) represents a hydroxyl group or a hydrolyzable group.
• the hydrolyzable group is not particularly limited and may be a known hydrolyzable group, for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy group, and the like.
• an alkoxy group, an acyloxy group, a ketoximate group, and an alkenyloxy group are preferred.
• an alkoxy group is more preferred, a methoxy group and an ethoxy group are even more preferred, and a methoxy group is particularly preferred.
• a plurality of X's are present, they may be the same as or different from each other.
• a represents any one of 0, 1, 2, and 3, and b represents any one of 0, 1, 2, and 3.
• a+b is 3 or less, and is preferably 3.
• b represents any one of 1, 2, and 3, and from the viewpoint of curability, it is preferably 2 or 3.
• the molecular weight of the silyl group-containing compound (E) is not particularly limited, and it may be a low molecular weight compound or a polymer.
• Patent Document 1 in the case of a low molecular weight silyl group-containing compound, it is possible to produce a silyl group-containing compound with less by-products, but in the case of a silyl group-containing compound with a large molecular weight, the selectivity of the silylated product is reduced.
• the catalyst and the production method of the present invention are particularly suitable for producing a silyl group-containing organic polymer ( Ea ) among the silyl group-containing compounds (E).
• the silyl group-containing organic polymer ( Ea ) is a hydrolyzable silyl group-containing organic polymer, it can be used as a curable resin for adhesives, sealing materials, elastic coating agents, pressure sensitive adhesives, etc., and is therefore industrially useful.
• the curable composition containing the hydrolyzable silyl group-containing organic polymer of the present invention exhibits superior curability, and furthermore, the rubber-like cured product obtained after curing can exhibit higher modulus, tensile strength, etc.
• the silyl group-containing organic polymer (E a ) has a polymer skeleton (also called a main chain structure) and a polymer chain end bonded to the polymer skeleton.
• the polymer skeleton is a structure in which a plurality of monomer units are formed in succession by bonding a plurality of monomers by addition, condensation, or the like.
• the monomer species contained in the polymer skeleton may be one type, or a mixture of a plurality of types may be bonded.
• the polymer chain end refers to a portion located at the end of the polymer backbone.
• the number of polymer chain ends of the silyl group-containing organic polymer (E a ) is 2 when the polymer backbone is entirely linear, and is 3 or more when the polymer backbone is entirely branched. When the polymer backbone is a mixture of linear and branched chains, the average number can be between 2 and 3.
• the silyl group of the silyl group-containing organic polymer (E a ) may be present in the polymer backbone and/or at the polymer chain end. In addition, two or more silyl groups may be present at one polymer chain end.
• the silyl group of the silyl group-containing organic polymer (E a ) is a hydrolyzable silyl group, it can be used as a curable resin such as an adhesive, a sealing material, an elastic coating agent, or a pressure sensitive adhesive, and the hydrolyzable silyl group is preferably contained in the polymer chain end of the silyl group-containing organic polymer (E a ).
• the polymer skeleton (also referred to as the main chain structure) of the silyl group-containing organic polymer (E a ) is not particularly limited, and various main chain structures can be used.
• the main chain structure include polyoxyalkylene polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymers, and polyoxypropylene-polyoxybutylene copolymers; hydrocarbon polymers such as ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; polyolefins obtained by condensation of dibasic acids such as adipic acid with glycols, or ring-opening polymerization of lactones; Examples of such polymers include ester polymers, (meth)acrylic acid ester polymers obtained by radical polymerization of
• saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth)acrylic acid ester polymers are preferred because they have relatively low glass transition temperatures and the resulting cured products have excellent cold resistance. Only one of these may be used, or two or more may be used in combination.
• silyl group-containing organic polymer (E a ) is a hydrolyzable silyl group-containing organic polymer
• polyoxyalkylene polymers and (meth)acrylic acid ester polymers are particularly preferred because they have high moisture permeability, excellent deep curing properties when made into a one-component curable composition, and also excellent adhesion.
• Polyoxyalkylene polymers are more preferred, and polyoxypropylene is even more preferred.
• the polyoxyalkylene polymer is preferably a polymer having a repeating unit represented by -R-O- (wherein R is a linear or branched alkylene group having 1 to 14 carbon atoms). R is more preferably a linear or branched alkylene group having 2 to 4 carbon atoms. Specific examples of the repeating unit represented by -R-O- include -CH 2 O-, -CH 2 CH 2 O-, -CH 2 CH(CH 3 )O-, -CH 2 CH(C 2 H 5 )O-, -CH 2 C(CH 3 )(CH 3 )O-, and -CH 2 CH 2 CH 2 CH 2 O- .
• the main chain structure of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units.
• silyl group-containing organic polymer (E a ) when the silyl group-containing organic polymer (E a ) according to this embodiment is a hydrolyzable silyl group-containing organic polymer and is used as a curable resin such as a sealant or adhesive, a polyoxypropylene-based polymer having oxypropylene repeating units in an amount of 50% by weight or more, more preferably 80% by weight or more, of the polymer skeleton is preferred because it is amorphous and has a relatively low viscosity.
• the main chain structure of the polyoxyalkylene polymer may be linear or may have branched chains. If it has branched chains, 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 branched chain (i.e., 3 terminal groups).
• 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 branched chain (i.e., 3 terminal groups).
• the polyoxyalkylene polymer is preferably one obtained by a ring-opening polymerization reaction of a cyclic ether compound using a polymerization catalyst in the presence of an initiator.
• cyclic ether compounds examples include ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used alone or in combination of two or more. Among the cyclic ether compounds, it is particularly preferable to use propylene oxide, since it gives an amorphous polyether polymer with a relatively low viscosity.
• initiators include alcohols such as butanol, ethylene glycol, propylene glycol, propylene glycol monoalkyl ether, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol, and sorbitol; and hydroxyl-terminated polyoxyalkylene polymers having a number average molecular weight of 300 to 4,000, such as polyoxypropylene diol, polyoxypropylene triol, polyoxyethylene diol, and polyoxyethylene triol.
• alcohols such as butanol, ethylene glycol, propylene glycol, propylene glycol monoalkyl ether, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glyco
• Examples of methods for synthesizing polyoxyalkylene polymers include, but are not limited to, a polymerization method using an alkaline catalyst such as KOH, a polymerization method using a transition metal compound-porphyrin complex catalyst such as the complex obtained by reacting an organoaluminum compound with porphyrin as disclosed in JP-A-61-215623, a polymerization method using a composite metal cyanide complex catalyst as disclosed in JP-B-46-27250, JP-B-59-15336, U.S. Pat. No. 3,278,457, U.S. Pat. No. 3,278,458, U.S. Pat. No. 3,278,459, U.S. Pat. No. 3,427,256, U.S.
• the silyl group-containing organic polymer (E a ) may be a polyoxyalkylene polymer containing other bonds such as urethane bonds and urea bonds in the polymer skeleton.
• the molecular weight distribution (Mw/Mn) of the silyl group-containing organic polymer ( Ea ) is not particularly limited, but is preferably 1.6 or less, more preferably 1.4 or less, even more preferably 1.3 or less, and particularly preferably 1.2 or less. Within the above range, the polymer has a relatively low viscosity and is easy to handle.
• the molecular weight distribution of the silyl group-containing organic polymer ( Ea ) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.
• the number average molecular weight of the silyl group-containing organic polymer (E a ) is preferably more than 3,000, more preferably more than 10,000, and even more preferably more than 20,000, as a polystyrene-equivalent molecular weight in GPC. When the number average molecular weight is large, the cured product exhibits high elongation and excellent mechanical properties. It is preferably 8,000 to 100,000, more preferably 8,000 to 50,000, and particularly preferably 8,000 to 35,000.
• a silyl group-containing organic polymer (E a ) can be obtained that exhibits excellent mechanical properties of the cured product, good curability, and has an easy-to-handle viscosity and excellent workability.
• the molecular weight of the silyl group-containing organic polymer (E a ) can also be expressed as an end group molecular weight calculated by directly measuring the end group concentration of a polymer precursor before the introduction of silyl groups by titration analysis based on the principles of the hydroxyl value measurement method of JIS K 1557-1 and the iodine value measurement method specified in JIS K 0070, and taking into consideration the structure of the organic polymer (degree of branching determined by the polymerization initiator used).
• the end group-converted molecular weight of the silyl group-containing organic polymer (E a ) can also be calculated by preparing a calibration curve of the number average molecular weight determined by general GPC measurement of the polymer precursor and the end group-converted molecular weight, and converting the number average molecular weight determined by GPC of the silyl group-containing organic polymer (E a ) into the end group-converted molecular weight.
• the allyl group-containing compound (C) is not particularly limited as long as it has an allyl group (CH 2 ⁇ CH—CH 2 —) and is capable of forming a silyl group-containing compound (E) by a hydrosilylation reaction with a hydrosilane compound (D).
• the allyl group-containing compound (C) may be an allyl group-containing organic polymer.
• the polymer backbone of the allyl group-containing organic polymer is the same as the polymer backbone of the silyl group-containing organic polymer (E a ), and therefore description thereof is omitted.
• the hydrosilane compound (D) according to the present embodiment is not particularly limited, but preferably has a structure represented by formula (2). SiR a X b H 4-ab formula (2)
• R, X, a, and b are as described above in relation to the general formula (1).
• hydrosilane compounds (D) include trimethoxysilane, triethoxysilane, triphenoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, (methoxymethyl)dimethoxysilane, (methoxymethyl)diethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-di ethylaminomethyl)diethoxysilane, diphenoxymethylsilane, methylsilane, dimethylsilane, trimethylsilane, ethylsilane, diethylsi
• trimethoxysilane and dimethoxymethylsilane are particularly preferred as the hydrosilane compound (D) in terms of curability and physical properties after curing.
• the amount (charge amount) of the hydrosilane compound (D) used in the reaction step is, in terms of the amount of substance, preferably 1 molar equivalent or more, preferably 3 molar equivalents or more, and more preferably 5 molar equivalents or more, relative to the allyl group possessed by the allyl group-containing compound (C). Also, it is usually 20 molar equivalents or less, preferably 10 molar equivalents or less.
• the silyl group can be introduced with high efficiency while suppressing the production cost.
• the viscosity of the silyl group-containing organic polymer (E a ) after production can be suppressed to a low level, and a polymer with good workability can be obtained.
• the amount (charge amount) of the ruthenium complex (A) used in the reaction step is, in weight ratio to the allyl group-containing compound (C), usually 0.01 ppm or more, preferably 0.1 ppm or more, more preferably 1 ppm or more, and usually 10% or less, preferably 1% or less, more preferably 0.1% or less.
• silyl groups can be introduced with high efficiency.
• the reaction process may use a solvent or may be solvent-free.
• a solvent there are no particular limitations on the type of solvent, and it is preferable that the solvent is a compound that does not react with the raw materials or catalyst. Specific examples include hydrocarbon solvents such as hexane, and halogen-based solvents such as dichloromethane. It is preferable to use a solvent that has been dehydrated and deoxygenated.
• the reaction temperature of the reaction process can be appropriately determined taking into consideration the reactivity (reaction rate) and the heat resistance temperature of the reaction vessel, but is usually 0°C or higher, preferably 20°C or higher, more preferably 40°C or higher, and usually 200°C or lower, preferably 150°C or lower.
• the reaction time is not particularly limited and may be about 5 minutes to 12 hours, or about 10 minutes to 5 hours.
• the reaction process is preferably carried out under an inert atmosphere such as nitrogen or argon.
• the ruthenium complex (A) and the compound (B) are added to the reaction system during the hydrosilylation reaction since this can improve the silylation rate.
• the ruthenium complex (A) contains a portion of ruthenium chloride (III)
• the ruthenium chloride (III) reacts with the added compound (B) and is converted to the ruthenium complex (A). Therefore, it is preferable for the ruthenium complex (A) and the compound (B) to come into contact with each other before the start of the hydrosilylation reaction.
• a method in which the ruthenium complex (A) and the compound (B) are added and mixed while stirring the allyl group-containing compound (C) charged in the reaction tank at a predetermined temperature, and then the hydrosilane compound (D) is added is given as an example of a preferred embodiment.
• the time interval between the addition of the ruthenium complex (A) and the compound (B) and the addition of the hydrosilane compound (D) is not particularly limited, and may be appropriately determined in consideration of the desired introduction rate of silyl groups, the time required for production, etc.
• the method for producing a silyl group-containing compound (E) also includes a step of mixing an allyl group-containing compound (C), a hydrosilane compound (D), a ruthenium compound (A') that does not have a compound (B) as a ligand, and a compound (B) to cause a hydrosilylation reaction.
• a ruthenium complex (A) synthesized in advance is not used, and a silylated product can be efficiently produced by mixing the ruthenium compound (A') and the compound (B) in a reaction tank to generate a ruthenium complex (A) in the system, which then functions as a catalyst.
• the allyl group-containing compound (C), the hydrosilane compound (D), and the compound (B) are as described above.
• the order of mixing the allyl group-containing compound (C), the hydrosilane compound (D), the ruthenium compound (A'), and the compound (B) is not particularly specified, and they can be mixed in any order.
• the "ruthenium compound (A')" and “reaction conditions” are described in detail below.
• the ruthenium compound (A') used in one embodiment of the present invention is not particularly limited except that it does not have compound (B) as a ligand.
• As the ruthenium compound (A'), ruthenium chloride (III) hydrate and a ruthenium complex having compound (B') as a ligand other than compound (B) can be used.
• Examples of the type of compound (B') include 2,5-norbornadiene ligand, 1,5-cyclooctadiene ligand, p-cymene ligand, mesitylene ligand, benzene ligand, carbonyl ligand, isocyanide ligand, arene ligand, and the like.
• the ruthenium compound (A') is a ruthenium complex having a ligand selected from a 2,5-norbornadiene ligand, a benzene ligand, and a p-cymene ligand.
• ⁇ Reaction conditions> The preferred conditions for the amount (charge 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 subjecting an allyl group-containing compound (C) and a hydrosilane compound (D) to a hydrosilylation reaction in the presence of a ruthenium complex (A)".
• the preferred amount (charge amount) of the ruthenium compound (A') used is the same as the above-mentioned amount (charge amount) of the ruthenium complex (A).
• This production method includes an operation of mixing the ruthenium compound (A') and the compound (B) in a reaction vessel to generate the ruthenium complex (A) in the system. Therefore, for example, it is preferable to add the ruthenium compound (A') and the compound (B) while stirring the allyl group-containing compound (C) charged in the reaction vessel at a predetermined temperature, and then add the hydrosilane compound (D).
• the time interval between the addition of the ruthenium compound (A′) and the compound (B) and the addition of the hydrosilane compound (D) is not particularly limited and may be appropriately determined in consideration of the desired introduction rate of silyl groups and the production time.
• the amount of compound (B) added is not particularly limited, and is usually 0.01 ppm or more, preferably 0.1 ppm or more, more preferably 1 ppm or more, and usually 10% or less, preferably 1% or less, more preferably 0.1% or less, by weight relative to the allyl group-containing compound (C).
• a mixture containing the silyl group-containing compound (E) and the ruthenium complex (A) can be obtained.
• a polymer mixture containing a hydrolyzable silyl group-containing polymer and a ruthenium complex (A) as the silyl group-containing organic polymer (E a ) can be used to form a curable composition by mixing a curing catalyst into the mixture.
• the content of the ruthenium complex (A) is equivalent to the amount (charge amount) of the ruthenium complex (A) or ruthenium compound (A') used.
• the content of the ruthenium complex (A) is, in terms of weight ratio, usually 0.01 ppm or more, preferably 0.1 ppm or more, more preferably 1 ppm or more, and usually 10% or less, preferably 1% or less, more preferably 0.1% or less, based on the hydrolyzable silyl group-containing polymer.
• a curable composition containing the silyl group-containing organic polymer can be formed.
• a cured product can be obtained by curing the curable composition.
• a polyoxyalkylene-based polymer is more preferable, and polyoxypropylene is even more preferable.
• the curable composition containing the hydrolyzable silyl group-containing organic polymer obtained by the manufacturing method described above has a short skinning time and exhibits good curing properties compared to hydrolyzable silyl group-containing organic polymers produced using conventionally known hydrosilylation reaction catalysts such as Karstedt's catalyst. Furthermore, the cured product obtained by curing the curable composition exhibits a high modulus and also exhibits high strength.
• the curable composition according to the present embodiment preferably contains a curing catalyst for the purpose of promoting the reaction of hydrolyzing and condensing the hydrolyzable silyl group, that is, the curing reaction.
• Curing catalysts that can be used include conventionally known catalysts, such as organotin compounds, metal carboxylates, amine compounds, carboxylic acids, alkoxy metals, inorganic acids, and mixtures thereof.
• organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), reaction products of dibutyltin oxide with silicate compounds, reaction products of dibutyltin oxide with phthalic acid esters, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate), dioctyltin distearate, dioctyltin oxide, and reaction products of dioctyltin oxide with silicate compounds.
• Dioctyltin compounds are preferred due to the growing concern about the environment
• metal carboxylates include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and calcium carboxylate.
• the carboxylic acid group can be a combination of the following carboxylic acids with various metals.
• 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.
• amines such as octylamine, 2-ethylhexylamine, laurylamine, stearylamine, piperidine, 4-methylpiperidine, and hexamethyleneimine
• nitrogen-containing heterocyclic compounds such
• carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.
• alkoxy metals include titanium compounds such as tetrabutyl titanate, titanium tetrakis(acetylacetonate), titanium ethylacetoacetate, and diisopropoxytitanium bis(ethylacetoacetate), aluminum compounds such as aluminum tris(acetylacetonate) and diisopropoxyaluminum ethylacetoacetate, and zirconium compounds such as zirconium tetrakis(acetylacetonate).
• titanium compounds such as tetrabutyl titanate, titanium tetrakis(acetylacetonate), titanium ethylacetoacetate, and diisopropoxytitanium bis(ethylacetoacetate
• aluminum compounds such as aluminum tris(acetylacetonate) and diisopropoxyaluminum ethylacetoacetate
• zirconium compounds such as zirconium tetrakis(acetylacetonate).
• curing catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.
• the curing catalyst may be a combination of two or more different catalysts.
• the combination of the above-mentioned amine compound and a carboxylic acid, or an amine compound and an alkoxy metal may have the effect of improving reactivity.
• the amount of the curing catalyst is 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, based on 100 parts by weight of the silyl group-containing organic polymer ( E a ) according to this embodiment. Furthermore, some curing catalysts may ooze out onto the surface of the cured product after the curable composition has cured, or may contaminate the surface of the cured product. In such cases, the amount of the curing catalyst used is set to 0.01 to 3.0 parts by weight, so that the surface condition of the cured product can be kept good while ensuring the curability.
• the curable composition according to this embodiment may contain other additives, such as silicon compounds, adhesion promoters, plasticizers, solvents, diluents, silicates, fillers, sagging inhibitors, antioxidants, light stabilizers, UV absorbers, physical property adjusters, tackifier resins, compounds containing epoxy groups, photocurable substances, oxygen curable substances, surface property improvers, epoxy resins, other resins, flame retardants, and foaming agents.
• the curable composition according to this embodiment may contain various additives as necessary for the purpose of adjusting the physical properties of the composition or the cured product. Examples of such additives include, for example, curability adjusters, radical inhibitors, metal deactivators, ozone inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments, and fungicides.
• the curable composition according to the present embodiment may contain various fillers, such as heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc oxide, PVC powder, PMMA powder, glass fiber and filament.
• various fillers such as heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc oxide, PVC powder, PMMA powder, glass fiber and filament.
• the amount of the filler used is preferably 1 to 300 parts by weight, and more preferably 10 to 250 parts by weight, based on 100 parts by weight of the silyl group-containing organic polymer (E a ) according to this embodiment.
• Balloons are spherical fillers that are hollow inside, and the materials for these balloons include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran.
• the amount of the balloons used is preferably 0.1 to 100 parts by weight, and more preferably 1 to 20 parts by weight, based on 100 parts by weight of the silyl group-containing organic polymer (E a ) according to this embodiment.
• An adhesion promoter may be added to the curable composition according to the present embodiment.
• a silane coupling agent or a reaction product of a silane coupling agent may be added.
• silane coupling agents include amino group-containing silanes such as ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane; ⁇ -isocyanatepropyltrimethoxysilane, ⁇ -isocyanatepropyltriethoxysilane, and ⁇ -isopropyltrimethoxysilane;
• the adhesive include isocyanate group-containing silanes such as isocyanate propyl methyl dimethoxy silane, ⁇ -isocyanate methyl trimethoxy si
• condensates of various silane coupling agents such as condensates of amino group-containing silanes and condensates of amino group-containing silanes and other alkoxy silanes; reactants of amino group-containing silanes and epoxy group-containing silanes, reactants of amino group-containing silanes and (meth)acrylic group-containing silanes, and other reactants of various silane coupling agents can also be used.
• the above adhesion promoters may be used alone or in combination of two or more.
• the amount of the silane coupling agent used is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the silyl group-containing organic polymer (E a ) according to this embodiment.
• plasticizer A plasticizer may be added to the curable composition according to this embodiment.
• the plasticizer 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)-1,4-benzenedicarboxylate; non-phthalate compounds such as 1,2-cyclohexanedicarboxylate diisononyl ester; aliphatic polycarboxylic acid ester compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, and acetyl tributyl citrate; unsaturated fatty acid ester compounds such as butyl oleate
• polymeric plasticizers can be used.
• polymeric plasticizers include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more, and polyethers such as derivatives in which the hydroxyl groups of these polyether polyols are converted to ester groups, ether groups, etc.; polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, etc.
• Plasticizers may be used alone or in combination of two or more kinds.
• the polymer plasticizer may not have a reactive silyl group, but may have a reactive silyl group. When it has a reactive silyl group, it acts as a reactive plasticizer and can prevent the plasticizer from migrating from the cured product. When it has a reactive silyl group, it is preferable that the number of reactive silyl groups is 1 or less, more preferably 0.8 or less, per molecule on average. When using a plasticizer having a reactive silyl group, particularly an oxyalkylene polymer having a reactive silyl group, its number average molecular weight is preferably lower than that of the silyl group-containing organic polymer (E a ).
• the amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and even more preferably 20 to 100 parts by weight, based on 100 parts by weight of the silyl group-containing organic polymer ( E a ) according to this embodiment.
• solvent or diluent may be added to the curable composition according to this embodiment.
• the solvent and diluent are not particularly limited, but may be an aliphatic hydrocarbon, an aromatic hydrocarbon, an alicyclic hydrocarbon, a halogenated hydrocarbon, an alcohol, an ester, a ketone, an ether, or the like.
• 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, in view of the problem of air pollution when the composition is used indoors.
• the above solvents or diluents may be used alone or in combination of two or more kinds.
• the curable composition according to the present embodiment may contain an anti-sagging agent to prevent sagging and improve workability as necessary.
• Anti-sagging agents are not particularly limited, but include, for example, polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sagging agents may be used alone or in combination of two or more.
• the amount of the sagging prevention agent used is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the silyl group-containing organic polymer (E a ) according to this embodiment.
• the curable composition according to the present embodiment may contain an antioxidant (antiaging agent).
• an antioxidant can improve the weather resistance of the cured product.
• examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols.
• Irganox 245, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 1330, and Irganox 1520 all manufactured by BASF
• SONGNOX 1076 manufactured by SONGWON
• BHT antioxidant
• hindered amine light stabilizers such as TINUVIN 622LD, TINUVIN 144, TINUVIN 292, CHIMASSORB 944LD, and CHIMASSORB 119FL (all manufactured by BASF); ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63, and ADK STAB LA-68 (all manufactured by ADEKA Corporation); SANOL LS-2626, SANOL LS-1114, and SANOL LS-744 (all manufactured by Sankyo Lifetech Co., Ltd.); and NOCRAC CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) can also be used.
• antioxidants such as SONGNOX 4120, Naugard 445, and OKABEST CLX050 can also be used. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731.
• the amount of the antioxidant used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the silyl group-containing organic polymer (E a ) according to this embodiment.
• a light stabilizer can be used in the curable composition according to the present embodiment.
• the use of a light stabilizer can prevent photo-oxidative deterioration of the cured product.
• Examples of light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based compounds, with hindered amine-based compounds being particularly preferred.
• the amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the silyl group-containing organic polymer (E a ) according to this embodiment.
• the curable composition according to the present embodiment can use an ultraviolet absorber.
• the use of an ultraviolet absorber can improve the surface weather resistance of the cured product.
• ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferred, and examples of such compounds include 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).
• the amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the silyl group-containing organic polymer (E a ) according to this embodiment.
• the curable composition according to the present embodiment may contain a physical property adjuster for adjusting the tensile properties of the resulting cured product as necessary.
• the physical property adjuster is not particularly limited, but examples thereof include alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane and phenyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and ⁇ -glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as tris(trimethylsilyl)borate and tris(triethylsilyl)
• the hardness of the curable composition according to the present embodiment can be increased when cured, or conversely, the hardness can be reduced and the breaking elongation can be increased.
• the physical property adjuster may be used alone or in combination of two or more kinds.
• compounds that produce compounds having monovalent silanol groups in the molecule upon hydrolysis have the effect of reducing the modulus of the cured product without increasing the stickiness of the surface of the cured product.
• Compounds that produce trimethylsilanol are particularly preferred.
• Examples of compounds that produce compounds having monovalent silanol groups in the molecule upon hydrolysis include silicon compounds that are derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, and that produce silane monool upon hydrolysis. Specific examples include phenoxytrimethylsilane, tris((trimethylsiloxy)methyl)propane, etc.
• the amount of the physical property adjuster used is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the silyl group-containing organic polymer (E a ) according to this embodiment.
• Tackifier resin A tackifier resin can be added to the curable composition according to the present embodiment for the purpose of increasing the adhesiveness or adhesion to the substrate or for other reasons as necessary. There are no particular limitations on the tackifier resin, and any commonly used tackifier resin can be used.
• terpene resins aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenol resins, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone-indene resins, rosin resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and their hydrogenated products, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, etc. These may be used alone or in combination of two or more.
• petroleum resins e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins,
• the amount of the tackifier 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, per 100 parts by weight of the silyl group-containing organic polymer ( E a ) according to this embodiment.
• a compound containing an epoxy group can be used in the curable composition according to the present embodiment.
• the use of a compound having an epoxy group can improve the restorability of the cured product.
• the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof.
• epoxy compound is preferably used in the range of 0.5 to 50 parts by weight per 100 parts by weight of the silyl group-containing organic polymer (E a ) according to the present embodiment.
• a photocurable material can be used in the curable composition according to the present embodiment.
• a photocurable material When a photocurable material is used, a film of the photocurable material is formed on the surface of the cured product, improving the stickiness and weather resistance of the cured product.
• Many compounds of this type are known, such as organic monomers, oligomers, resins, or compositions containing them.
• Representative compounds that can be used include unsaturated acrylic compounds, which are monomers, oligomers, or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, polyvinyl cinnamates, or azido resins.
• the amount of the photocurable substance used is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the silyl group-containing organic polymer (E a ) according to this embodiment.
• oxygen-curable substances An oxygen-curable substance can be used in the curable composition according to the present embodiment.
• oxygen-curable substances include unsaturated compounds that can react with oxygen in the air, which react with oxygen in the air to form a cured film near the surface of the cured product, preventing the surface from becoming sticky and preventing dirt and dust from adhering to the surface of the cured product.
• oxygen-curable substances include drying oils such as tung oil and linseed oil, and various alkyd resins obtained by modifying these compounds; acrylic polymers, epoxy resins, and silicone resins modified with drying oils; and liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, and polymers of C5 to C8 dienes obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene. These may be used alone or in combination of two or more types.
• the amount of the 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, per 100 parts by weight of the silyl group-containing organic polymer (E a ) according to this embodiment.
• the oxygen-curing substance is preferably used in combination with a photocuring substance.
• the curable composition according to the present embodiment can be used in combination with an epoxy resin.
• the composition to which an epoxy resin is added is particularly preferred as an adhesive, particularly as an adhesive for exterior wall tiles.
• Examples of the epoxy resin include bisphenol A type epoxy resins and novolac type epoxy resins.
• a curing agent that cures the epoxy resin can be used in combination with the curable composition according to this embodiment.
• the epoxy resin curing agent that can be used, and any commonly used epoxy resin curing agent can be used.
• the amount used is preferably in the range of 0.1 to 300 parts by weight per 100 parts by weight of epoxy resin.
• the curable composition according to the present embodiment can be prepared as a one-component type in which all ingredients are mixed in advance and stored in a sealed state, and then cured by moisture in the air after application, or as a two-component type in which ingredients such as a curing catalyst, a filler, a plasticizer, and water are mixed separately as a curing agent, and the ingredients are mixed with the organic polymer composition before use. From the viewpoint of workability, the one-component type is preferred.
• the curable composition is a one-component type
• all of the ingredients are mixed in advance, so it is preferable to dehydrate and dry ingredients that contain water before use, or to dehydrate them by reducing pressure during mixing.
• storage stability can be further improved by adding an alkoxysilane compound such as methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldiethoxysilane, or ⁇ -glycidoxypropyltrimethoxysilane.
• an alkoxysilane compound such as methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ -mercapto
• the curable composition according to the present embodiment can be used as a pressure-sensitive adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a waterproofing material, a coating waterproofing material, a mold release agent, an anti-vibration material, a vibration-damping material, a soundproofing material, a foaming material, a paint, a spraying material, etc.
• the cured product obtained by curing the curable composition according to the present embodiment has excellent flexibility and adhesiveness, and can therefore be suitably used as a sealing material or an adhesive.
• the curable composition according to this embodiment can be used in a wide variety of applications, including electrical and electronic component materials such as solar cell backside sealing materials, electrical and electronic components such as insulating coating materials for electric wires and cables, electrical insulating materials for devices, acoustic insulating materials, elastic adhesives, binders, contact adhesives, spray-type sealants, crack repair materials, tiling adhesives, adhesives for asphalt waterproofing materials, powder coatings, casting materials, medical rubber materials, medical adhesives, medical adhesive sheets, medical device sealants, dental impression materials, food packaging materials, and joint sealants for exterior materials such as sizing boards.
• electrical and electronic component materials such as solar cell backside sealing materials, electrical and electronic components such as insulating coating materials for electric wires and cables, electrical insulating materials for devices, acoustic insulating materials, elastic adhesives, binders, contact adhesives, spray-type sealants, crack repair materials, tiling adhesives, adhesives for asphalt waterproofing materials, powder coatings, casting materials, medical rubber materials, medical
• sealing materials can be used for various applications such as sealing materials, coating materials, anti-slip coating materials, buffer materials, primers, conductive materials for electromagnetic wave shielding, thermally conductive materials, hot melt materials, potting agents for electrical and electronic devices, films, gaskets, concrete reinforcing materials, temporary adhesives, various molding materials, and sealing materials for rust prevention and waterproofing of wired glass and laminated glass end faces (cut parts), liquid sealants used in automobile parts, large vehicle parts such as trucks and buses, train car parts, aircraft parts, ship parts, electrical parts, various machine parts, etc.
• the curable composition according to the present embodiment can also be used as an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiling, an adhesive for stone veneer, an adhesive for ceiling finishing, an adhesive for floor finishing, an adhesive for wall finishing, an adhesive for vehicle panels, an adhesive for assembling electrical, electronic and precision equipment, an adhesive for bonding leather, textile products, fabric, paper, boards and rubber, a reactive post-crosslinking pressure-sensitive adhesive, a sealant for direct glazing, a sealant for double-glazing, a sealant for SSG construction, or a sealant for working joints in buildings, and a material for civil engineering and bridge construction. It can also be used as an adhesive material such as an adhesive tape or an adhesive sheet.
• the electron-withdrawing group is at least one selected from the group consisting of a fluoro group, a bromo group, and an iodo group.
• the ruthenium complex (A) according to item 2 wherein the compound (B) is at least one selected from the group consisting of 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene, and 1,3,5-tribromobenzene.
• [Item 6] 4.
• the ruthenium complex (A) according to item 3 wherein the compound (B) is 2,3-dibromonorbornadiene.
• a hydrosilylation reaction catalyst comprising the ruthenium complex (A) according to any one of items 1 to 6.
• a method for producing a silyl group-containing compound (E), comprising a step of mixing an allyl group-containing compound (C), a hydrosilane compound (D), and the hydrosilylation reaction catalyst according to Item 7, and carrying out a hydrosilylation reaction.
• [Item 9] 9. The method according to item 8, wherein a compound (B) is further mixed in the hydrosilylation reaction.
• a method for producing a silyl group-containing compound (E), comprising a step of mixing an allyl group-containing compound (C), a hydrosilane compound (D), a ruthenium compound (A') not having compound (B) as a ligand, and compound (B) to carry out a hydrosilylation reaction, A production method in which compound (B) has at least one carbon-carbon double bond in one molecule, and an electron-withdrawing group is bonded to at least one of the carbon atoms forming the carbon-carbon double bond. [Item 11] 11.
• silyl group-containing compound (E) is a hydrolyzable silyl group-containing polyoxyalkylene polymer.
• compound (B) has a benzene ring skeleton as the skeleton containing the carbon-carbon double bond.
• compound (B) has a norbornadiene skeleton as the skeleton containing the carbon-carbon double bond.
• compound (B) has a norbornadiene skeleton as the skeleton containing the carbon-carbon double bond.
• [Item 20] 20. The method according to any one of Items 10 to 19, wherein the ruthenium compound (A') has a ligand selected from 2,5-norbornadiene, benzene, and p-cymene.
• [Item 21] A polymer mixture comprising a hydrolyzable silyl group-containing polymer and the ruthenium complex (A) according to any one of items 1 to 6.
• a curable composition comprising the polymer mixture according to item 21 and a curing catalyst.
• [Item 23] 23 A cured product obtained by curing the curable composition according to item 22.
• the present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
• the number average molecular weight in the examples is a GPC molecular weight measured under the following conditions.
• Liquid delivery system Tosoh HLC-8420GPC Column: Tosoh TSKgel Super H series Solvent: THF (tetrahydrofuran) Molecular weight: polystyrene equivalent Measurement temperature: 40°C
• the proportion of silyl groups, 1-propenyl groups, or hydrogenated products was calculated by 1 H NMR measurement using the following nuclear magnetic resonance (NMR) apparatus.
• Example 1 While stirring an ethanol solution containing 0.15 g of ruthenium chloride (III) hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.), which is the ruthenium compound (A'), under a nitrogen atmosphere, 0.064 g of sodium carbonate and 0.20 g of 2,3-dibromonorbornadiene (manufactured by Tokyo Chemical Industry Co., Ltd.), which is the compound (B), were added under heating and 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), which is the ruthenium complex (A).
• ruthenium chloride (III) hydrate manufactured by Tokyo Chemical Industry Co., Ltd.
• B 2,3-dibromonorbornadiene
• Example 2 While stirring an ethanol solution containing 0.15 g of ruthenium chloride (III) hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.), which is the ruthenium compound (A'), under a nitrogen atmosphere, 0.064 g of sodium carbonate and 0.36 g of 2,3-dibromonorbornadiene (manufactured by Tokyo Chemical Industry Co., Ltd.), which is the compound (B), were added under heating and 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), which is the ruthenium complex (A).
• III ruthenium chloride
• A' ruthenium compound
• B 2,3-dibromonorbornadiene
• the obtained unpurified allyl-terminated polyoxypropylene was mixed and stirred with n-hexane and water, and then the water was removed by centrifugation.
• the hexane was distilled off under reduced pressure from the obtained hexane solution to remove the metal salts in the polymer.
• an allyl-containing organic polymer (C-1) was obtained, which is an allyl-containing compound (C).
• the number-average molecular weight of the polymer was 3,100.
• Example 3 To the polymer (C-1) which is the allyl group-containing compound (C), 2,400 ppm of the ruthenium complex (A-1) which is the ruthenium complex (A) obtained in Example 1 and dimethoxymethylsilane (5.0 molar equivalents relative to the allyl groups in the polymer (C-1)) which is the hydrosilane compound (D) were added, and a hydrosilylation reaction was carried out at 70°C. The reaction was continued until it was confirmed that the allyl groups in the polymer (C-1) had been completely consumed by performing 1 H NMR measurement every hour from the start of the reaction, and then the volatile components were distilled off under reduced pressure to obtain a polymer which is the silyl group-containing compound (E). The obtained polymer was subjected to 1 H NMR measurement to calculate the ratio of each group to the total of the silyl group, 1-propenyl group, and hydrogenated product. The results are shown in Table 1.
• Example 4 A hydrosilylation reaction was carried out in the same manner as in Example 3, except that 2,400 ppm of ruthenium complex (A-2), which is the ruthenium complex (A) obtained in Example 2, was used. The results are shown in Table 1.
• Examples 5 to 17 To the polymer (C-1) which is the allyl group-containing compound (C), the ruthenium complex (A) or each ruthenium compound (A') and each compound (B) were added as shown in Table 1, and the mixture was stirred at 70°C for 10 minutes. Furthermore, dimethoxymethylsilane (5.0 molar equivalents relative to the allyl groups in the polymer (C-1)) which is the hydrosilane compound (D) was added, and the allyl groups in the polymer (C-1) were subjected to a hydrosilylation reaction at 70°C.
• Example 3 which uses ruthenium complex (A-1), with Example 5, which uses ruthenium complex (A-1) and also 2,3-dibromonorbornadiene as compound (B), it is clear that silyl groups were introduced more selectively in Example 5.
• Example 6 in which [RuCl 2 (nbd)] n was used as the ruthenium compound (A') and 2,3-dibromonorbornadiene was added as the compound (B), with Comparative Examples 7 to 12, in which [RuCl 2 (nbd)] n was used as the ruthenium compound (A') and a compound (B') not corresponding to the compound (B) was added, it can be seen that Example 6 was able to introduce silyl groups more selectively to the allyl groups of the polymer (C-1).
• Example 18 To the polymer (C-2) which is the allyl group-containing compound (C), 240 ppm of the ruthenium complex (A-2) which is the ruthenium complex (A) obtained in Example 2 was added, and further dimethoxymethylsilane (5.0 molar equivalents relative to the allyl groups in the polymer (C-2)) which is the hydrosilane compound (D) was added, and a hydrosilylation reaction was carried out on the allyl groups in the polymer (C-2) at 90°C.
• Example 19 To the polymer (C-2) which is the allyl group-containing compound (C), 240 ppm of [RuCl 2 (nbd)] n which is the ruthenium compound (A') and 620 ppm of 2,3-dibromonorbornadiene which is the compound (B) were added, and the mixture was stirred at 90°C for 10 minutes. Furthermore, dimethoxymethylsilane (5.0 molar equivalents relative to the allyl groups in the polymer (C-2)) which is the hydrosilane compound (D) was added, and a hydrosilylation reaction was carried out on the allyl groups in the polymer (C-2) at 90°C.
• dimethoxymethylsilane 5.0 molar equivalents relative to the allyl groups in the polymer (C-2)
• D hydrosilane compound
• Example 20 To the polymer (C-3) which is the allyl group-containing compound (C), 240 ppm of the ruthenium complex (A-2) which is the ruthenium complex (A) obtained in Example 2, and dimethoxymethylsilane (5.0 molar equivalents relative to the allyl groups in the polymer (C-3)) which is the hydrosilane compound (D) were added, and a hydrosilylation reaction was carried out on the allyl groups in the polymer (C-3) at 90° C.
• each ruthenium compound (A') and each compound (B) were added as shown in Table 4, and the mixture was stirred at 90°C for 10 minutes. Furthermore, dimethoxymethylsilane (5.0 molar equivalents relative to the allyl groups in the polymer (C-3)) which is the hydrosilane compound (D) was added, and the allyl groups in the polymer (C-3) were subjected to a hydrosilylation reaction at 90°C.
• Example 26 To the polymer (C-2) which is the allyl group-containing compound (C) obtained in Synthesis Example 2, 240 ppm of [RuCl 2 (nbd)] n which is the ruthenium compound (A') and 620 ppm of 2,3-dibromonorbornadiene which is the compound (B) were added, and the mixture was stirred at 100° C. for 10 minutes. Furthermore, triethoxysilane (5.0 molar equivalents relative to the allyl groups in the polymer (C-2)) which is the hydrosilane compound (D) was added, and a hydrosilylation reaction was carried out on the allyl groups in the polymer (C-2) at 100° C.
• Example 26 silyl groups were introduced more selectively to the allyl groups of the allyl group-containing organic polymer than in Comparative Example 18. Therefore, it was confirmed that a high silyl group introduction rate can be achieved by carrying out a hydrosilylation reaction using the production method of the present invention even for other types of hydrosilane compounds.
• Example 27 To 1-octene (1.0 g, 8.9 mmol) which is the allyl group-containing compound (C), 2 mg of the ruthenium complex (A-2) which is the ruthenium complex (A) obtained in Example 2 was added while stirring at 60° C., and further dimethoxymethylsilane (1.4 g, 13.4 mmol) which is the hydrosilane compound (D) was added, and a hydrosilylation reaction of the allyl group in 1-octene was carried out at 60° C. 1 H NMR measurement was carried out, and it was confirmed that the allyl group in 1-octene was completely consumed in 30 minutes, and a silylated product was produced in a yield of 99% or more. It was therefore confirmed that the production method of the present invention can be applied without any problems even when the allyl group-containing compound (C) is a low molecular weight compound that is not a polymer.
• Example 28 In an atmosphere of 23° C. and 50% relative humidity, 100 parts by weight of the hydrolyzable silyl group-containing organic polymer (E-1) which is the silyl group-containing compound (E) obtained in Example 19 was mixed with 90 parts by weight of DINP (diisononyl phthalate, manufactured by J-Plus Corporation), 160 parts by weight of Hakuenka CCR (precipitated calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd.), and 100 parts by weight of 1,2-diphenylmethane (1,2-diphenylmethane) ...
• DINP diisononyl phthalate, manufactured by J-Plus Corporation
• Hakuenka CCR precipitated calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd.
• the obtained curable composition was filled into a mold about 5 mm thick with a spatula under an atmosphere of 23°C and 50% relative humidity, and the time when the surface was smoothed to a flat shape was defined as the curing start time, and the time when the composition to be evaluated no longer adhered to the spatula when the surface was touched with the spatula was defined as the skinning time.
• the results are shown in Table 6.
• the obtained curable composition was filled into a mold and aged for 2 days at 23°C and 50% relative humidity, and then for another 2 days at 50°C to produce a sheet-like cured product with a thickness of about 3 mm.
• the sheet-like cured product was punched into a No. 3 dumbbell shape and subjected to a tensile strength test in an atmosphere of 23°C and 50% relative humidity to measure the modulus at 50% and 100% elongation (M50 and M100).
• M50 and M100 modulus at 50% and 100% elongation
• the strength at break (TB) and elongation (EB) were measured.
• the measurement was performed at a tensile speed of 200 mm/min using an autograph (AGS-J) manufactured by Shimadzu Corporation. The results are shown in Table 6.
• Example 29 A curable composition was obtained in the same manner as in Example 28, except that 100 parts by weight of the hydrolyzable silyl group-containing organic polymer (E-2), which is the silyl group-containing compound (E) obtained in Example 20, was used instead of 100 parts by weight of the hydrolyzable silyl group-containing organic polymer (E-1). Using the obtained curable composition, the skinning time and dumbbell tensile properties were evaluated in the same manner as in Example 28. The results are shown in Table 6.
• Example 20 A curable composition was obtained in the same manner as in Example 28, except that 100 parts by weight of the hydrolyzable silyl group-containing organic polymer (E'-2) obtained in Comparative Example 15 was used instead of 100 parts by weight of the hydrolyzable silyl group-containing organic polymer (E-1).
• the obtained curable composition was used to evaluate the skinning time and dumbbell tensile properties in the same manner as in Example 28. The results are shown in Table 6.
• the hydrolyzable silyl group-containing organic polymer (E-1) obtained by the manufacturing method of the present invention showed a shorter skinning time and better curing properties than the hydrolyzable silyl group-containing organic polymer (E'-1) produced using the same allyl group-containing organic polymer (C-2) as a raw material and a Karstedt catalyst. Furthermore, the modulus and strength increased, with M100 being about 1.6 times and the strength being about 1.1 times.
• the hydrolyzable silyl group-containing organic polymer (E-2) obtained by the manufacturing method of the present invention showed a shorter skinning time and better curing properties than the hydrolyzable silyl group-containing organic polymer (E'-2) produced using the same allyl group-containing organic polymer (C-3) as a raw material and a Karstedt catalyst. Furthermore, the modulus and strength increased. M100 was about 1.7 times and the strength was about 1.3 times.
• the resulting unpurified methallyl group-containing organic polymer was mixed and stirred with n-hexane and water, and then the water was removed by centrifugation.
• the hexane was distilled off under reduced pressure from the resulting hexane solution to remove the metal salts in the polymer.
• G-1 methallyl group-containing organic polymer
• Example 30 Using a 5 L planetary mixer (manufactured by Dalton Co., Ltd.), one-component curable compositions were prepared according to the formulations 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: surface-untreated heavy calcium carbonate), and 20 parts by weight of Ti-Pure R-902+ (manufactured by Chemours: titanium oxide) were dried under reduced pressure at 120° C. for 2 hours.
• Ultra-Pflex manufactured by Specialty Minerals: colloidal calcium carbonate
• Q3T manufactured by Huber: surface-untreated heavy calcium carbonate
• Ti-Pure R-902+ manufactured by Chemours: titanium oxide
• the resulting mixture was taken out and passed through a three-roll mill once to uniformly disperse, and then the mixture was charged again into the mixer and dehydrated under reduced pressure for 2 hours. After dehydration under reduced pressure, the mixture was cooled to 50°C or lower, and then 3 parts by weight of A-171 (manufactured by Momentive: vinyltrimethoxysilane), 3 parts by weight of A-1120 (manufactured by Momentive: N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane), and 2 parts by weight of Neostan U-220H (manufactured by Nitto Kasei Co., Ltd., dibutyltin bis(acetylacetonate)) were added and kneaded for 3 minutes. Subsequently, the mixture was degassed under reduced pressure for 2 minutes, and the resulting mixture was immediately filled into a moisture-proof aluminum cartridge and sealed to obtain a curable composition.
• A-171 manufactured by Moment
• the obtained curable composition was filled into a mold about 5 mm thick with a spatula under an atmosphere of 23°C and 50% relative humidity, and the time when the surface was smoothed to a flat shape was defined as the curing start time, and the time when the composition to be evaluated no longer adhered to the spatula when the surface was touched with the spatula was defined as the skinning time.
• the results are shown in Table 7.
• the obtained curable composition was filled into a mold and aged for 3 days at 23°C and 50% relative humidity, and then for 4 days at 50°C to produce a sheet-like cured product with a thickness of about 3 mm.
• the sheet-like cured product was punched into a No. 3 dumbbell shape and subjected to a tensile strength test in an atmosphere of 23°C and 50% relative humidity to measure the modulus at 50% and 100% elongation (M50 and M100).
• M50 and M100 modulus at 50% and 100% elongation
• the strength at break (TB) and elongation (EB) were measured.
• the measurement was performed at a tensile speed of 200 mm/min using an autograph (AGS-J) manufactured by Shimadzu Corporation. The results are shown in Table 7.
• the obtained curable composition was filled into a sheet-shaped mold having a thickness of 3 mm at 23° C. and a relative humidity of 50%. After curing for 3 days at 23° C. and a relative humidity of 50%, the composition was aged in a 50° C. dryer for 4 days to obtain a sheet-shaped cured product. The obtained cured product was punched into a dumbbell shape (JIS A type) for a tear test to obtain a test piece. The obtained test piece was subjected to a tear test (tensile speed 200 mm/min) using an autograph at 23° C. and a relative humidity of 50%, and the stress at break (TB) was measured.
• a tear test tensile speed 200 mm/min
• the above-mentioned curable composition was applied to an aluminum material as an adherend with a thickness of 50 ⁇ m and an adhesive area of 25 mm x 25 mm, and after an open time of 2 minutes, the adherends were bonded together.
• the obtained test specimen was left at a constant temperature and humidity of 23°C and 50%.
• a tensile shear test (tensile speed 50 mm/min) was performed using an autograph to measure the stress at break (TB).
• Example 21 A curable composition was obtained in the same manner as in Example 30, except that 100 parts by weight of the hydrolyzable silyl group-containing organic polymer (E'-2) obtained in Comparative Example 15 was used instead of 100 parts by weight of the hydrolyzable silyl group-containing organic polymer (E-3).
• E'-2 the hydrolyzable silyl group-containing organic polymer obtained in Comparative Example 15 was used instead of 100 parts by weight of the hydrolyzable silyl group-containing organic polymer (E-3).
• the skinning 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.
• the hydrolyzable silyl group-containing organic polymer (E-3) obtained by the manufacturing method of the present invention showed a shorter skinning time and better curing properties than the hydrolyzable silyl group-containing organic polymer (E'-2) produced using the same allyl group-containing organic polymer (C-3) as a raw material and a Karstedt catalyst, and the hydrolyzable silyl group-containing organic polymer (E'-3) produced using the methallyl group-containing organic polymer (G-1) as a raw material and a Karstedt catalyst. It also showed better tear strength and tensile shear strength.
• the hydrolyzable silyl group-containing organic polymer (E-3) showed a higher modulus and strength than the hydrolyzable silyl group-containing organic polymer (E'-2), and showed values comparable to those of the hydrolyzable silyl group-containing organic polymer (E'-3).
• silyl groups were able to be introduced highly selectively in all of Examples 31 to 34.
• the greater the molar equivalent of the hydrosilane compound (D) relative to the allyl group in the polymer (C-3) the higher the introduction rate of the silyl group and the lower the viscosity of the hydrolyzable silyl group-containing organic polymer.
• Example 31 in which 5 molar equivalents of hydrosilane compound (D) was reacted with respect to the allyl groups in polymer (C-3), a polymer having the highest silylation rate and the lowest viscosity in Table 8 was obtained.
• Example 32 in which the polymer (C-3) was reacted with 3 molar equivalents of the hydrosilane compound (D) based on the allyl groups in the polymer (C-3), the silylation rate was lower and the viscosity after silylation was higher than those in Example 31. However, a polymer having a lower viscosity was obtained as compared with that in Example 33, in which the polymer (C-3) was reacted with 2 molar equivalents of the hydrosilane compound (D) based on the allyl groups in the polymer (C-3).

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