WO2022181545A1

WO2022181545A1 - Manufacturing method for polymer comprising hydrolyzable silyl group, and polymer, curable composition, and cured product

Info

Publication number: WO2022181545A1
Application number: PCT/JP2022/006967
Authority: WO
Inventors: 直己味岡; 章徳佐藤; のどか久保田
Original assignee: 株式会社カネカ
Priority date: 2021-02-24
Filing date: 2022-02-21
Publication date: 2022-09-01

Abstract

According to the present invention, a polymer comprising a hydrolyzable silyl group is manufactured by causing a silane compound comprising a hydrolyzable group or a hydroxyl group and a vinyl group on a silicon atom to undergo a metathesis reaction with a polymer comprising a vinyl group in the presence of a catalyst. Among the hydrolyzable silyl groups comprised by the polymer, 80 mol% or more have a structure represented by the formula: -CH=CH-Si(R1)3-a(X)a. In the formula, R1 represents a substituted or unsubstituted 1-20C hydrocarbon group; X represents a hydroxyl group or a hydrolyzable group; and a represents 1, 2, or 3.

Description

Method for producing polymer having hydrolyzable silyl group, polymer, curable composition, and cured product

The present invention relates to a method for producing a polymer having a hydrolyzable silyl group, a polyoxyalkylene polymer having a hydrolyzable silyl group, a curable composition containing the polymer, and a cured product thereof.

An organic polymer having a hydroxyl group or a hydrolyzable group on a silicon atom and having a silicon-containing group capable of forming a siloxane bond (hereinafter referred to as a "hydrolyzable silyl group") is known as a moisture-reactive polymer. It is contained in many industrial products such as adhesives, sealants, coating materials, paints, and adhesives, and is used in a wide range of fields. As such a hydrolyzable silyl group-containing polymer, various polymers having a main chain skeleton such as a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a (meth)acrylic acid ester copolymer are known. ing.

As a method for producing a hydrolyzable silyl group-containing polymer, for example, after synthesizing a polyoxyalkylene polymer having a terminal hydroxyl group by ring-opening polymerization of an epoxy compound, the hydroxyl group is converted into a carbon-carbon double bond. A method of introducing a hydrolyzable silyl group into a polymer by converting the carbon-carbon double bond and a silane compound into a hydrosilylation reaction is known (see, for example, Patent Document 1). However, the hydrolyzable silyl group-containing polymer obtained by this method does not always have sufficient curability, and improvement of this is desired.

In Patent Document 2, a hydroxyl group possessed by a polyoxyalkylene polymer is converted to a carbon-carbon triple bond, and then the carbon-carbon triple bond is subjected to a hydrosilylation reaction with a silane compound to convert a hydrolyzable silyl group into the polymer. A method of introduction is described, and the resulting polymer is said to have carbon-carbon double bonds attached to silicon atoms and to exhibit rapid curing properties.

JP-A-52-73998 WO2019/189491

According to the production method described in Patent Document 2, although a fast-curing hydrolyzable silyl group-containing polymer can be produced, in introducing a carbon-carbon triple bond, the carbon-carbon is unstable and difficult to handle. It was necessary to use triple bond containing compounds (eg propargyl bromide). Therefore, development of a new production method that does not use the compound is desired.

In view of the above situation, the present invention provides a novel method for producing a polymer having a hydrolyzable silyl group and a carbon-carbon double bond bonded to a silicon atom in the silyl group, and a method obtainable by the production method. An object of the present invention is to provide a polymer, a curable composition containing the polymer, and a cured product thereof.

The present inventors used a metathesis reaction that recombines bonds between vinyl groups instead of a hydrosilylation reaction on a carbon-carbon triple bond as described in Patent Document 2 to obtain a hydrolyzable silyl group, The inventors have found that it is possible to produce a polymer having a carbon-carbon double bond bonded to the silicon atom in the silyl group, leading to the present invention.

That is, the present invention provides a hydrolyzable silyl polymer comprising a step of metathesis reacting a vinyl group-containing polymer with a silane compound having a vinyl group and a hydroxyl group or a hydrolyzable group on a silicon atom in the presence of a catalyst. The present invention relates to a method for producing a polymer having groups.
Preferably, the temperature during the metathesis reaction is 60° C. or less.
Preferably, the metathesis reaction is carried out while bubbling an inert gas through the reaction system.
Preferably, said catalyst is a Grubbs catalyst.
Preferably, the silane compound is represented by the formula: CH ₂ ═CH—Si(R ¹ ) _3-a (X) _a (wherein R ¹ is a substituted or unsubstituted represents a hydrocarbon group, X represents a hydroxyl group or a hydrolyzable group, and a represents 1, 2, or 3).
The present invention also provides a polyoxyalkylene polymer having hydrolyzable silyl groups, wherein 80 mol% or more of the hydrolyzable silyl groups are represented by the formula: -CH=CH-Si(R ¹ ) _{3- a} (X) having _a structure represented by a (wherein R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; X represents a hydroxyl group or a hydrolyzable group; a represents 1, 2, or 3), and also relates to polyoxyalkylene-based polymers.
Preferably, the structure is represented by -O-CH ₂ -CH=CH-Si(R ¹ ) _3-a (X) _a .
The polyoxyalkylene polymer may contain ruthenium, in which case the ruthenium content in the polymer may be 10 to 2,000 ppm.
Furthermore, the present invention also relates to a curable composition containing the polyoxyalkylene polymer. The curable composition may further contain a curing catalyst.
Furthermore, the present invention also relates to a cured product of the curable composition.

According to the present invention, a novel process for producing a polymer having a hydrolyzable silyl group and a carbon-carbon double bond bonded to a silicon atom in the silyl group, and a polymer obtainable by the process , a curable composition containing the polymer, and a cured product thereof.
According to the present invention, hydrolyzable silyl groups and carbon-carbon double bonds attached to silicon atoms in the silyl groups are prepared without the use of unstable and difficult-to-handle carbon-carbon triple bond-containing compounds. It is possible to produce a polymer having
Moreover, according to the present invention, a polymer in which a hydrolyzable silyl group is bonded to the polymer skeleton via a carbon-carbon double bond can be produced with high selectivity.

Embodiments of the present invention are described in detail below.
This embodiment includes a step of metathesis reacting a polymer having a vinyl group with a silane compound having a vinyl group and a hydroxyl group or a hydrolyzable group on a silicon atom in the presence of a catalyst. It relates to a method for producing a polymer having A metathesis reaction is a reaction in which bond recombination proceeds between two types of olefins. A hydrolyzable silyl group can be introduced into the polymer by recombination of the bond between the vinyl group of the polymer and the vinyl group of the silane compound by the metathesis reaction.

(Polymer having a vinyl group)
The starting polymer has vinyl groups. The vinyl group can be represented by CH ₂ =CH-. The vinyl group may be directly attached to the polymer backbone, or may be attached to the polymer backbone via a linking group, for example, as an allyl group (CH ₂ =CH-CH ₂ -). good. The position where the vinyl group is bonded is not particularly limited. The polymer is preferably an organic polymer. The organic polymer has a polymer skeleton composed of a plurality of repeating units. The polymer backbone of the organic polymer may be linear or branched.

The polymer skeleton of the organic polymer is not particularly limited, and various polymer skeletons can be used. Specific examples of polymer backbones include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymers, and polyoxypropylene-polyoxybutylene copolymers. ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, etc., copolymers of polychloroprene, polyisoprene, isoprene or butadiene with acrylonitrile and/or styrene, etc. Saturated hydrocarbon polymers such as coalescence, polybutadiene, isoprene or copolymers of butadiene with acrylonitrile and styrene, and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; Coalescence; (meth)acrylic acid ester-based polymers obtained by radical polymerization of (meth)acrylic acid ester-based monomers such as ethyl (meth)acrylate and butyl (meth)acrylate, as well as (meth)acrylic acid-based monomers and acetic acid Vinyl polymers such as polymers obtained by radical polymerization of monomers such as vinyl, acrylonitrile, and styrene; graft polymers obtained by polymerizing vinyl monomers in the above polymers; polysulfide polymers; polyamides type polymer; polycarbonate type polymer; diallyl phthalate type polymer; and other organic polymers. Each of the above polymers may be mixed in block form, graft form, or the like. Among these, saturated hydrocarbon-based polymers, polyoxyalkylene-based polymers, and (meth)acrylic acid ester-based polymers have relatively low glass transition temperatures, and the obtained cured products have excellent cold resistance. are preferred, polyoxyalkylene-based polymers are more preferred, and polyoxypropylene is particularly preferred.

The organic polymer may be a polymer having one type of polymer skeleton, or a mixture of two or more types of polymers having different polymer skeletons. The mixture may be a mixture of polymers produced separately, or a mixture produced at the same time so as to have an arbitrary composition.

The number average molecular weight of the organic polymer is not particularly limited. ,000 to 30,000. When the number average molecular weight is 3,000 or more, the relative amount of hydrolyzable silyl groups with respect to the whole polymer is within an appropriate range, which is desirable in terms of production cost. Moreover, when the number average molecular weight is 100,000 or less, it is easy to achieve a desired viscosity from the viewpoint of workability. The number average molecular weight can be determined in terms of polystyrene by GPC measurement.

Although the molecular weight distribution (Mw/Mn) of the organic polymer is not particularly limited, it is preferably narrow. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, still more preferably 1.5 or less, and particularly preferably 1.4 or less. Moreover, from the viewpoint of improving mechanical properties such as durability and elongation of the cured product, it is preferably 1.2 or less. The molecular weight distribution (Mw/Mn) can be calculated from the number-average molecular weight and the weight-average molecular weight obtained in terms of polystyrene by GPC measurement.

<Method for producing polymer>
Next, a method for producing a polymer having a vinyl group will be described. The production method is not particularly limited, but may be, for example, a method of introducing a carbon-carbon double bond into a hydroxyl-containing organic polymer by utilizing the reactivity of hydroxyl groups.

(Polyoxyalkylene polymer)
Hereinafter, an example of a method for producing the organic polymer will be described in detail in the case where the polymer skeleton of the organic polymer is a polyoxyalkylene polymer. The method for producing the organic polymer is described below. is not limited to

(polymerization)
The polymer skeleton of the polyoxyalkylene-based polymer can be formed by polymerizing an epoxy compound with an initiator having a hydroxyl group by a conventionally known method, whereby a hydroxyl-terminated polyoxyalkylene-based polymer is obtained. . Although the specific polymerization method is not particularly limited, since a hydroxyl group-terminated polymer with a small molecular weight distribution (Mw/Mn) can be obtained, a polymerization method using a double metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex is used. is preferred.

Examples of hydroxyl-containing initiators include, but are not limited to, ethylene glycol, propylene glycol, glycerin, pentaerythritol, low-molecular-weight polyoxypropylene glycol, low-molecular-weight polyoxypropylene triol, allyl alcohol, and low-molecular-weight polyoxypropylene. Organic compounds having one or more hydroxyl groups, such as monoallyl ethers and low-molecular-weight polyoxypropylene monoalkyl ethers, can be mentioned.

Although the epoxy compound is not particularly limited, examples thereof include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and butyl glycidyl ether. Propylene oxide is preferred.

(Reaction with alkali metal salt)
In introducing a carbon-carbon double bond to a hydroxyl-terminated polyoxyalkylene polymer, first, an alkali metal salt is allowed to act on the hydroxyl-terminated polyoxyalkylene polymer to convert the terminal hydroxyl group to a metaloxy group. preferably. A double metal cyanide complex catalyst can also be used instead of the alkali metal salt. As described above, a metaloxy group-terminated polyoxyalkylene polymer is formed.

Although the alkali metal salt is not particularly limited, examples thereof include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. Sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferred from the viewpoint of ease of handling and solubility, and sodium methoxide and sodium tert. -butoxide is more preferred. From the standpoint of availability, sodium methoxide is particularly preferred, and from the standpoint of reactivity, sodium tert-butoxide is particularly preferred. The alkali metal salt may be dissolved in a solvent before being subjected to the reaction.

The amount of the alkali metal salt used is not particularly limited, but the molar ratio to the hydroxyl group of the hydroxyl-terminated polyoxyalkylene polymer is preferably 0.5 or more, more preferably 0.6 or more, and 0.7 or more. More preferably, 0.8 or more is even more preferable. The molar ratio is preferably 1.2 or less, more preferably 1.1 or less.

The alkali metal salt is used to convert the hydroxyl groups of the hydroxyl-terminated polyoxyalkylene polymer into metaloxy groups. It is preferable to previously remove substances having a hydroxyl group other than coalescence from the reaction system. For removal, known methods may be used, such as heat evaporation, vacuum devolatilization, spray vaporization, thin film evaporation, azeotropic devolatilization, and the like.

The temperature at which the alkali metal salt is allowed to act can be appropriately set by those skilled in the art, but is preferably 50°C or higher and 150°C or lower, more preferably 110°C or higher and 145°C or lower. The time for which the alkali metal salt is allowed to act is preferably 10 minutes or more and 5 hours or less, more preferably 30 minutes or more and 3 hours or less.

(Reaction with electrophile)
By reacting an electrophilic agent having a vinyl group on the metaloxy group-terminated polyoxyalkylene polymer obtained as described above, the metaloxy group can be converted to a structure containing a vinyl group. . Thereby, a polyoxyalkylene polymer having a vinyl group is formed.

The electrophile having a vinyl group is not particularly limited as long as it is a compound capable of reacting with the metaloxy group possessed by the polyoxyalkylene polymer and introducing a vinyl group into the polyoxyalkylene polymer. group-containing organic halides, and the like.

The organic halide having a vinyl group can react with the metaloxy group through a halogen substitution reaction to form an ether bond, thereby introducing a structure containing a vinyl group to the end of the polyoxyalkylene polymer. . The organic halide having a vinyl group is, but not limited to, the following general formula (3):
Z—R ³ —CH═CH ₂ (3)
can be expressed as In general formula (3), R ³ represents a direct bond or a divalent hydrocarbon group having 1 to 4 carbon atoms. Z represents a halogen atom.

R ³ is preferably a divalent hydrocarbon group having 1 to 3 carbon atoms, more preferably a divalent hydrocarbon group having 1 to 2 carbon atoms. The hydrocarbon group is preferably an alkylene group, and a methylene group, ethylene group, propylene group, or butylene group can be used. Methylene groups are particularly preferred.

Specific examples of organic halides having a vinyl group are not particularly limited, but include vinyl chloride, allyl chloride, vinyl bromide, allyl bromide, vinyl iodide, and allyl iodide. Allyl chloride is preferred for ease of handling.

The amount of the organic halide having a vinyl group to be added is not particularly limited, but the molar ratio of the organic halide to the hydroxyl group of the polyoxyalkylene polymer is preferably 0.7 or more, more preferably 1.0 or more. . Moreover, the molar ratio is preferably 5.0 or less, more preferably 2.0 or less.

The temperature at which the vinyl group-containing organic halide is reacted with the metaloxy group-terminated polyoxyalkylene polymer is preferably 50°C or higher and 150°C or lower, more preferably 110°C or higher and 140°C or lower. The reaction time is preferably 10 minutes to 5 hours, more preferably 30 minutes to 3 hours.

((Meth)acrylic acid ester polymer)
When the polymer skeleton of the organic polymer is a (meth)acrylic acid ester polymer, the method for producing the organic polymer includes (I) a compound having a polymerizable unsaturated group and a reactive functional group (for example, , acrylic acid, 2-hydroxyethyl acrylate) are copolymerized with a monomer having a (meth)acrylic structure to obtain a polymer, and then any position in the resulting polymer (preferably the molecular chain end ), and (II) a monomer having a (meth)acrylic structure is polymerized by a living radical polymerization method such as atom transfer radical polymerization to obtain a polymer. A method of introducing a vinyl group at a certain position (preferably at a molecular chain terminal), and the like can be mentioned.

(Saturated hydrocarbon polymer)
When the main chain of the organic polymer is a saturated hydrocarbon polymer, the method for producing the organic polymer includes olefins having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene, and isobutylene. Examples include a method of polymerizing a base compound as a main monomer to obtain a polymer, and then introducing a vinyl group at any position (preferably at the molecular chain terminal) of the obtained polymer.

(Silane compound having vinyl group and hydroxyl group or hydrolyzable group on silicon atom)
The silane compound having a vinyl group and a hydroxyl group or a hydrolyzable group on the silicon atom (hereinafter also referred to as a silane compound for short) has a vinyl group bonded to the silicon atom and a hydroxyl group or a hydrolyzable group bonded to the silicon atom. is a compound having Specifically, the silane compound can be represented by the formula: CH ₂ ═CH—Si(R ¹ ) _3-a (X) _a .

R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms is preferably 1 to 10, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. When the hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include halogen groups such as chloro, alkoxy groups such as methoxy, and amino groups such as N,N-diethylamino. .

Examples of R ¹ include unsubstituted groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-hexyl group, 2-ethylhexyl group and n-dodecyl group. Alkyl group; chloromethyl group, methoxymethyl group, substituted alkyl group such as N,N-diethylaminomethyl group; vinyl group, isopropenyl group, unsaturated hydrocarbon group such as allyl group; cycloalkyl group such as cyclohexyl group; phenyl aryl groups such as toluyl group and 1-naphthyl group; and aralkyl groups such as benzyl group. Preferred are substituted or unsubstituted alkyl groups, more preferred are methyl groups, ethyl groups, chloromethyl groups and methoxymethyl groups, still more preferred are methyl groups and methoxymethyl groups, and particularly preferred are methyl groups. is the base. As R ¹ , only one type of group may be used, or two or more types of groups may be used in combination.

　X represents a hydroxyl group or a hydrolyzable group. Examples of X include hydroxyl group, hydrogen, halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group and alkenyloxy group. The above alkoxy group and the like may have a substituent. An alkoxy group is preferred because it is moderately hydrolyzable and easy to handle, methoxy, ethoxy, n-propoxy and isopropoxy are more preferred, methoxy and ethoxy are still more preferred, and methoxy is particularly preferred. As X, only one type of group may be used, or two or more types of groups may be used in combination.

"a" in the above formula represents 1, 2, or 3. Preferably 2 or 3. It is more preferably 2 in terms of the balance between the curability of the polymer and the physical properties of the cured product.

Specific examples of the silane compound include trimethoxyvinylsilane, triethoxyvinylsilane, tris(2-propenyloxy)vinylsilane, triacetoxyvinylsilane, methyldimethoxyvinylsilane, methyldiethoxyvinylsilane, dimethoxyethylvinylsilane, (chloromethyl)dimethoxy vinylsilane, (chloromethyl)diethoxyvinylsilane, (methoxymethyl)dimethoxyvinylsilane, (methoxymethyl)diethoxyvinylsilane, (N,N-diethylaminomethyl)dimethoxyvinylsilane, (N,N-diethylaminomethyl)diethoxyvinylsilane and the like. be done. One type of silane compound may be used alone, or two or more types may be used in combination.

The amount of the silane compound used is not particularly limited, but it is preferably 0.1 to 100 times by moles, more preferably 0.5 to 30 times by moles, more preferably 1 to 20 times by moles the vinyl groups possessed by the polymer. Molar fold is more preferred. From the viewpoint of increasing the rate of silyl group introduction into the polymer, it is preferably 2 mol times or more, more preferably 3 mol times or more.

(catalyst)
The catalyst is a catalyst that promotes a metathesis reaction between the vinyl group of the polymer and the vinyl group of the silane compound. Although the catalyst is not particularly limited, an organometallic complex having carbene as a ligand can be used. Metal species constituting the metal complex include, for example, titanium, tantalum, molybdenum, tungsten, ruthenium, and osmium. Ruthenium carbene complexes are particularly preferred, and specifically, first-generation Grubbs catalysts (benzylidene-bis(tricyclohexylphosphino)dichlororuthenium), second-generation Grubbs catalysts ([1,3-bis-(2, 4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylmethylene)(tricyclohexylphosphino)ruthenium), first generation Hoveyda-Grubbs catalyst (dichloro(o-isopropoxyphenylmethylene) (tri Cyclohexylphosphine)ruthenium(II)), second-generation Hoveyda-Grubbs catalyst ([1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(o-isopropoxyphenylmethylene) ruthenium) and the like. Of these, Grubbs catalysts are preferred, and first-generation Grubbs catalysts are particularly preferred, since they improve the rate of introduction of silyl groups into the polymer. As the catalyst, only one type may be used, or two or more types may be used in combination.

The amount of the catalyst used is not particularly limited, but it is preferably 0.001 to 1 mol, more preferably 0.01 to 0.5 mol, more preferably 0.01 to 1 mol, relative to the vinyl groups of the polymer. 05 to 0.3 mol times is more preferable.

(Metathesis reaction)
The polymer having a vinyl group is subjected to a metathesis reaction with a silane compound having a vinyl group and a hydroxyl group or a hydrolyzable group on the silicon atom in the presence of the catalyst to obtain a polymer having a hydrolyzable silyl group. Coalescence can be produced. A hydrolyzable silyl group is introduced into the polymer by recombination of bonds between the vinyl group of the polymer and the vinyl group of the silane compound by the metathesis reaction. As an example, the reaction formula in the case where the polymer having a vinyl group is polyoxypropylene having an allyl group and the silane compound is trimethoxyvinylsilane is shown below.

PPO in the formula represents polyoxypropylene, and Me represents a methyl group. Although the product polymer having a hydrolyzable silyl group is shown in the trans form, the structure of the polymer is not limited to the trans form, and may include both the trans and cis forms.

The reaction temperature during the metathesis reaction is not particularly limited, and may be, for example, about 0 to 150°C, preferably about 15 to 120°C. However, from the viewpoint of suppressing the isomerization reaction of the allyl group, which is a side reaction, the temperature is preferably relatively low, specifically 80°C or lower, more preferably 60°C or lower, and particularly preferably 50°C or lower. . The reaction time of the metathesis reaction is not particularly limited, and may be, for example, about 1 to 10 hours.

The metathesis reaction may be carried out in the presence of a solvent or may be carried out without a solvent. When a solvent is used, the type of solvent is not particularly limited and may be selected as appropriate. Hydrogen, aliphatic halogenated hydrocarbons such as dichloroethane and chloroform, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and isopropylbenzene, aromatic halogenated hydrocarbons such as chlorobenzene and chlorotoluene, methanol and ethanol and ether solvents such as tetrahydrofuran (THF) and tetrahydropyran (THP). As the solvent, only one type may be used, or two or more types may be used in combination.

The metathesis reaction may be carried out by mixing each component and stirring. In this case, the metathesis reaction is preferably carried out while bubbling an inert gas such as nitrogen or argon into the reaction system, since the rate of introduction of silyl groups into the polymer is improved. It is presumed that this is because the bubbling of the inert gas efficiently removes ethylene, which is a by-product, from the reaction system.

In the metathesis reaction, a polymer formed by coupling two molecules of a polymer having a vinyl group may be produced as a by-product.

(Polymer having a hydrolyzable silyl group)
A polymer having a hydrolyzable silyl group can be produced by the production method detailed above. Such polymers also constitute one aspect of the present embodiment. However, the polymer is not limited to the production method according to this embodiment.

The polymer having a hydrolyzable silyl group has a hydrolyzable silyl group and a carbon-carbon double bond bonded to a silicon atom in the silyl group. Thus, the polymer that can be produced according to this embodiment can exhibit rapid curing properties due to the carbon-carbon double bond attached to the silicon atom in the hydrolyzable silyl group.

The hydrolyzable silyl group possessed by the polymer corresponds to the hydrolyzable silyl group in the silane compound and can be represented by —Si(R ¹ ) _3-a (X) _a . wherein R ¹ , X, and a are each as described above. Specific examples of the hydrolyzable silyl group possessed by the polymer include, for example, a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a methyldimethoxysilyl group, a methyldi ethoxysilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl) ) dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group and the like. Only one type of hydrolyzable silyl group may be used, or two or more types may coexist.

According to a preferred embodiment, the hydrolyzable silyl group-containing polymer has a hydrolyzable silyl group bonded to the polymer skeleton via a carbon-carbon double bond, as shown in the chemical reaction formula. Specifically, it may have a structure represented by the formula: —CH═CH—Si(R ¹ ) _3-a (X) _a . R ¹ , X, and a in the above formula are each as described above.

According to the method of introducing a hydrolyzable silyl group into the polymer by hydrosilylating the carbon-carbon triple bond of the polymer with a silane compound, as described in Patent Document 2, the following chemical reaction formula can be obtained. As shown, in addition to the structure represented by the formula: -CH=CH-Si(R ¹ ) _3-a (X) _a (hereinafter also referred to as the β-form structure), the formula: -C(=CH ₂ )(—Si(R ¹ ) _3-a (X) _a ) (hereinafter also referred to as α-form structure) can also be formed. That is, according to a conventionally known production method, a mixture containing a polymer molecule having a β-body structure and a polymer molecule having an α-body structure at a ratio of approximately 1:1 is produced.

On the other hand, according to the present embodiment, due to the reaction mechanism of the metathesis reaction, the β-body structure is formed with high selectivity, and the α-body structure cannot be substantially formed. Therefore, in the polymer having a hydrolyzable silyl group that can be produced according to the present embodiment, the proportion of the hydrolyzable silyl groups occupied by the β-form structure is preferably 80 mol% or more and 100 mol% or less, more preferably is 90 mol% or more and 100 mol% or less, more preferably 95 mol% or more and 100 mol% or less, and the ratio of the α-body structure is preferably 0 mol% or more and 20 mol% or less, more preferably 0 mol%. 10 mol % or more, more preferably 0 mol % or more and 5 mol % or less. Polymers having such a high ratio of 80 mol % or more of β-body structure have not been reported so far.

According to a preferred embodiment, the structure represented by the formula: -CH=CH-Si(R ¹ ) _3-a (X) _a is represented by -O-CH ₂ -CH=CH-Si(R ¹ ) _3- It may be a structure represented by _a (X) _a . Such a structure can be formed by using an allyl group-containing polymer as the vinyl group-containing polymer.

The details of the polymer skeleton, the number average molecular weight, and the range of the molecular weight distribution of the polymer having the hydrolyzable silyl group are the same as those of the polymer having the vinyl group, so the description is omitted.

When the polymer having a hydrolyzable silyl group is produced using a ruthenium-containing catalyst as a catalyst, the polymer may contain ruthenium derived from the catalyst. In such a case, the ruthenium content of the polymer having a hydrolyzable silyl group is not particularly limited, depending on the amount of the ruthenium-containing catalyst used, the method of post-treatment, etc., but is, for example, 10 to 2,000 ppm. can be to some extent. The lower limit may be 100 ppm or more, 500 ppm or more, or 1,000 ppm or more.
The ruthenium content ratio may be calculated from the amount of the ruthenium-containing catalyst used, or may be measured by general elemental analysis such as mass spectrometry.

(Curable composition)
A polymer having a hydrolyzable silyl group as described above can constitute a curable composition containing it.

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

As the curing catalyst, conventionally known ones can be used. Specifically, organic tin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, alkoxy metals, inorganic acids, etc. can be used.

Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), dibutyltin oxide and silicate compounds. reaction product with dibutyltin oxide and phthalate ester, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate) phosphate), dioctyltin dilaurate, dioctyltin distearate, dioctyltin diacetate, dioctyltin oxide, a reaction product of dioctyltin oxide and a silicate compound, and the like. Dioctyltin compounds are preferred due to recent heightened environmental concerns.
However, since the polymer according to this embodiment can exhibit rapid curing properties, the curable composition according to this embodiment does not contain an organic tin compound and is generally less active than an organic tin compound. A curing catalyst (in particular, an amine compound or the like) may be contained. Even if the curable composition according to the present embodiment contains an amine compound, it can exhibit good curability.

Specific examples of carboxylate metal salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and calcium carboxylate. As the carboxylic acid group, the following carboxylic acid and various metals can be combined.

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

Specific examples of carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.

Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate, titanium tetrakis (acetylacetonate), diisopropoxytitanium bis (ethylacetonate), aluminum tris (acetylacetonate), diisopropoxy aluminum ethylacetate Examples include aluminum compounds such as acetate, and zirconium compounds such as zirconium tetrakis (acetylacetonate).

As other curing catalysts, fluorine anion-containing compounds, photoacid generators, and photobase generators can also be used.

The curing catalyst may be used in combination of two or more different catalysts. For example, the combination of the amine compound and carboxylic acid, or the combination of the amine compound and alkoxy metal provides the effect of improving the reactivity. There is a possibility that it will be

In addition, since the hydrolyzable silyl group of the polymer according to the present embodiment has high activity, the amount of the curing catalyst can be reduced, or a curing catalyst with low activity can be used, or an amino group-containing silane coupling agent. Aminosilanes can also be used as curing catalysts. Since aminosilane is usually added as an adhesion imparting agent in many cases, when aminosilane is used as a curing catalyst, a curable composition that does not use a commonly used curing catalyst can be produced. Therefore, it is preferable not to add other curing catalysts. In particular, when the hydrolyzable silyl group contains a trimethoxysilyl group or a methoxymethyldimethoxysilyl group, excellent curability is exhibited even when only aminosilane is used as a curing catalyst.

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 0.01 to 10 parts by weight with respect to 100 parts by weight of the polymer according to the present embodiment. is particularly preferred. If the amount of the curing catalyst is less than 0.001 part by weight, the reaction rate may be insufficient. On the other hand, when the amount of the curing catalyst exceeds 20 parts by weight, the reaction rate is too fast, and the usable time of the composition is shortened, resulting in poor workability and poor storage stability. Furthermore, some curing catalysts may exude to the surface of the cured product or contaminate the surface of the cured product after the curable composition is cured. In such a case, by setting the amount of the curing catalyst to 0.01 to 3.0 parts by weight, it is possible to maintain good surface conditions of the cured product while ensuring curability.

The curable composition according to the present embodiment contains other additives such as a silicon compound, an adhesion imparting agent, a plasticizer, a solvent, a diluent, a silicate, a filler, an anti-sagging agent, an antioxidant, and a light stabilizer. , UV absorbers, physical property modifiers, tackifier resins, compounds containing epoxy groups, photo-curing substances, oxygen-curing substances, surface property modifiers, epoxy resins, other resins, flame retardants, foaming agents. can be In addition, various additives may be added to the curable composition according to the present embodiment as necessary for the purpose of adjusting various physical properties of the composition or cured product. Examples of such additives include curability modifiers, radical inhibitors, metal deactivators, antiozonants, phosphorus peroxide decomposers, lubricants, pigments, antifungal agents, and the like. be done.

(filler)
Various fillers can be added to the curable composition according to the present embodiment. Fillers include ground 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, active zinc white, PVC powder, PMMA powder, glass fiber and filament, and the like.

The amount of filler used is preferably 1 to 300 parts by weight, more preferably 10 to 250 parts by weight, with respect to 100 parts by weight of the polymer according to this embodiment.

Organic balloons and inorganic balloons may be added for the purpose of weight reduction (lower specific gravity) of the composition. The balloon is hollow inside with a spherical filler, and is made of inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran. materials.

The amount of balloon used is preferably 0.1 to 100 parts by weight, more preferably 1 to 20 parts by weight, with respect to 100 parts by weight of the polymer according to this embodiment.

(Adhesion imparting agent)
An adhesion imparting agent can be added to the curable composition according to the present embodiment. A silane coupling agent or a reactant of the silane coupling agent can be added as the adhesion imparting agent.
Specific examples of silane coupling agents include γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ- Amino group-containing silanes such as aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane; isocyanate group-containing silanes such as ethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, α-isocyanatomethyltrimethoxysilane, α-isocyanatomethyldimethoxymethylsilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercapto group-containing silanes such as γ-mercaptopropylmethyldimethoxysilane; epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; . Condensates of various silane coupling agents such as condensation products of amino group-containing silanes, condensation products of amino group-containing silanes and other alkoxysilanes; reaction products of amino group-containing silanes and epoxy group-containing silanes; Reaction products of various silane coupling agents, such as reaction products of containing silanes and (meth)acrylic group-containing silanes, can also be used. The adhesiveness-imparting agent 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, more preferably 0.5 to 10 parts by weight, with respect to 100 parts by weight of the polymer according to this embodiment.

(Plasticizer)
A plasticizer can be added to the curable composition according to the present embodiment. Specific examples of plasticizers include dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), phthalate compounds such as butylbenzyl phthalate; bis(2-ethylhexyl )-terephthalate compounds such as 1,4-benzenedicarboxylate; non-phthalate compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, Aliphatic polyvalent carboxylic acid ester compounds such as tributyl acetylcitrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; phenyl alkylsulfonic acid esters; phosphoric acid ester compounds; trimellitic acid ester compounds; Paraffin; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxystearate;

In addition, a polymer plasticizer can be used. Specific examples of 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; polyethers such as derivatives converted to polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like. A plasticizer may be used individually and may use 2 or more types together.

The amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and even more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the polymer according to this embodiment.

(solvent, diluent)
A solvent or diluent can be added to the curable composition according to the present embodiment. Solvents and diluents that can be used include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, and ethers. When a solvent or diluent is used, 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, because 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.

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

The amount of anti-sagging agent used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymer according to this embodiment.

(Antioxidant)
An antioxidant (antiaging agent) can be used in the curable composition according to the present embodiment. The use of an antioxidant can enhance the weather resistance of the cured product. Examples of antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. 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, more preferably 0.2 to 5 parts by weight, with respect to 100 parts by weight of the polymer according to this embodiment.

(light stabilizer)
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. Benzotriazole-based, hindered amine-based, and benzoate-based compounds can be exemplified as light stabilizers, and hindered amine-based compounds are particularly preferred.

The amount of light stabilizer used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, with respect to 100 parts by weight of the polymer according to the present embodiment.

(Ultraviolet absorber)
A UV absorber can be used in the curable composition according to the present embodiment. The use of an ultraviolet absorber can enhance the surface weather resistance of the cured product. Examples of UV absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based, and metal chelate-based compounds. Benzotriazole-based compounds are particularly preferred, and are commercially available under the names Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571, Tinuvin 1600, Tinuvin B75 (manufactured by BASF).
The amount of the ultraviolet absorbent used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, with respect to 100 parts by weight of the polymer according to this embodiment.

(Physical property modifier)
A physical property modifier for adjusting the tensile properties of the resulting cured product may be added to the curable composition according to the present embodiment, if necessary. Although the physical property modifier is not particularly limited, for example, alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane. arylalkoxysilanes such as; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as silyl)borate; silicone varnishes; polysiloxanes; By using the physical property modifier, the hardness of the cured curable composition according to the present embodiment can be increased, or conversely, the hardness can be decreased to increase elongation at break. The physical property modifiers may be used alone or in combination of two or more.

In particular, a compound that produces a compound having a monovalent silanol group in the molecule by hydrolysis has the effect of lowering the modulus of the cured product without worsening the surface stickiness of the cured product. Compounds that generate trimethylsilanol are particularly preferred. Examples of compounds that generate a compound having a monovalent silanol group in the molecule by hydrolysis include alcohol derivatives such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, which are hydrolyzed into silane monovalent groups. Mention may be made of silicon compounds that produce ols. Specific examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.

The amount of the physical property modifier used is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, with respect to 100 parts by weight of the polymer according to the present embodiment.

(tackifying resin)
A tackifying resin can be added to the curable composition according to the present embodiment for the purpose of enhancing the adhesiveness or adhesion to a substrate, or for other purposes. As the tackifying resin, there is no particular limitation, and those commonly used can be used.

Specific examples include terpene-based resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenolic resins, phenolic resins, modified phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins, coumarone-indene resins, rosin-based Resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and hydrogenated products thereof, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, and the like. These may be used alone or in combination of two or more.

The amount of the tackifying resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, and more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polymer according to the present embodiment. More preferred.

(Compound containing an epoxy group)
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 enhance the restorability of the cured product. Examples of compounds having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxyoctyl stearate, epoxy butyl stearate and the like. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight with respect to 100 parts by weight of the polymer according to this embodiment.

(Photocurable substance)
A photocurable substance can be used in the curable composition according to the present embodiment. When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved. Many compounds such as organic monomers, oligomers, resins, or compositions containing them are known as this type of compound. Unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, etc., which are monomers, oligomers, or mixtures thereof can be used.

The amount of the photocurable substance used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer according to this embodiment.

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

The amount of the oxygen-curable 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 polymer according to this embodiment. As described in JP-A-3-160053, oxygen-curable substances are preferably used in combination with photo-curable substances.

(Epoxy resin)
An epoxy resin can be used in combination with the curable composition according to the present embodiment. A composition containing an epoxy resin is particularly preferred as an adhesive, especially an adhesive for exterior wall tiles. Examples of epoxy resins include bisphenol A type epoxy resins and novolac type epoxy resins.

The weight ratio of the epoxy resin to the polymer according to the present embodiment is preferably in the range of polymer according to the present embodiment/epoxy resin=100/1 to 1/100. If the ratio of the polymer according to the present embodiment/epoxy resin is less than 1/100, it becomes difficult to obtain the effect of improving the impact strength and toughness of the cured epoxy resin, and the polymer/epoxy resin according to the present embodiment becomes difficult to obtain. exceeds 100/1, the strength of the cured polymer becomes insufficient.

When an epoxy resin is added, a curing agent that cures the epoxy resin can be used in combination with the curable composition according to the present embodiment. The epoxy resin curing agent that can be used is not particularly limited, and generally used epoxy resin curing agents can be used.

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

<<Preparation of curable composition>>
The curable composition according to the present embodiment can be prepared as a one-component type in which all the ingredients are preformed and sealed and cured by moisture in the air after application, and a curing catalyst is separately added as a curing agent. , a filler, a plasticizer, water, etc., and mixed with the organic polymer composition before use. From the viewpoint of workability, the one-component type is preferred.

When the curable composition is a one-component type, since all the ingredients are pre-blended, the ingredients containing water are preliminarily dehydrated and dried before use, or dehydrated by decompression or the like during blending and kneading. is preferred. In addition to the dehydration drying method, methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, Addition of alkoxysilane compounds such as ethoxysilane and γ-glycidoxypropyltrimethoxysilane further improves the storage stability.

<Application>
The curable composition according to the present embodiment includes adhesives, sealing materials for buildings, ships, automobiles, roads, etc., adhesives, waterproofing materials, coating film waterproofing materials, molding agents, vibration-proof materials, vibration-damping materials, Can be used as soundproofing material, foaming material, paint, spraying material. A cured product obtained by curing the curable composition according to the present embodiment is excellent in flexibility and adhesiveness, and thus can be suitably used as a sealant or an adhesive.

In addition, the curable composition according to the present embodiment can be used for 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, and acoustic insulation. Materials, elastic adhesives, binders, contact adhesives, spray sealing materials, crack repairing materials, tiling adhesives, asphalt waterproofing adhesives, powder coatings, casting materials, medical rubber materials, medical Adhesives, medical adhesive sheets, sealing materials for medical equipment, dental impression materials, food packaging materials, joint sealing materials for exterior materials such as sizing boards, coating materials, anti-slip coating materials, cushioning materials, primers, electro-conductive materials for shielding electromagnetic waves Materials, thermally conductive materials, hot melt materials, potting agents for electric and electronic devices, films, gaskets, concrete reinforcing materials, adhesives for temporary fixing, various molding materials, and protection of wire glass and laminated glass edge faces (cut parts) Various applications such as sealing materials for rust and waterproofing, automotive parts, large vehicle parts such as trucks and buses, parts for train cars, aircraft parts, marine parts, electrical parts, and liquid sealants used in various machine parts. available for Taking automobiles as an example, it can be used in a wide variety of ways, such as adhesive attachment of plastic covers, trims, flanges, bumpers, windows, interior members, and exterior parts. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, resin moldings, etc. alone or with the help of a primer, it can be used as various types of sealing compositions and adhesive compositions. . Further, the curable composition according to the present embodiment is an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiling, an adhesive for stone, a ceiling finishing adhesive, a floor finishing adhesive, a wall Finishing adhesives, vehicle panel adhesives, electrical, electronic and precision equipment assembly adhesives, adhesives for bonding leather, textiles, fabrics, paper, boards and rubber, reactive post-crosslinking pressure sensitive adhesives , a sealing material for direct glazing, a sealing material for double glazing, a sealing material for the SSG construction method, a sealing material for working joints of buildings, a material for civil engineering, and a bridge material. Furthermore, it can be used as an adhesive material such as an adhesive tape and an adhesive sheet.

The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

The number average molecular weight in the examples is the GPC molecular weight measured under the following conditions.
Liquid delivery system: Tosoh HLC-8420GPC
Column: TSKgel SuperH series manufactured by Tosoh Solvent: THF
Molecular weight: Polystyrene equivalent Measurement temperature: 40°C

The "silyl group introduction rate" was calculated by the following formula using the integrated value of the signal representing each group after measuring ¹ H NMR for the polyoxyalkylene polymer having a hydrolyzable silyl group.
Formula: 100 × (number of moles of carbon-carbon double bonds next to hydrolyzable silyl groups) / (number of moles of carbon-carbon double bonds next to hydrolyzable silyl groups and hydrolyzable silyl groups introduced The number of moles of a group capable of introducing a hydrolyzable silyl group (allyl group in this example) that remained without being removed, and the isomerized group (1 in this example, 1 -propenyl group), the number of moles of a group (a propyl group in this example) obtained by reducing the group into which the hydrolyzable silyl group can be introduced, and the groups into which the hydrolyzable silyl group can be introduced. is the total number of moles of carbon-carbon double bonds formed by coupling)

The "molar ratio of the α-body structure and the β-body structure" is obtained by measuring ¹ H NMR of the polyoxyalkylene polymer having a hydrolyzable silyl group, and calculating the integrated value of the signals indicated by the α-body structure and the β-body structure. It was calculated by the following formula.
Mole ratio of α-form structure = (number of moles of carbon-carbon double bonds adjacent to hydrolyzable silyl groups of α-form structure)/(moles of carbon-carbon double bonds adjacent to hydrolyzable silyl groups of α-form structure number + number of moles of carbon-carbon double bonds next to hydrolyzable silyl groups in β-body structure)
Mole ratio of β-form structure = (moles of carbon-carbon double bonds adjacent to hydrolyzable silyl groups in β-form structure)/(moles of carbon-carbon double bonds adjacent to hydrolyzable silyl groups in α-form structure number + number of moles of carbon-carbon double bonds next to hydrolyzable silyl groups in β-body structure)

The "ruthenium content ratio" was calculated by the following procedure.
First, the weight of ruthenium is calculated from the weight of the catalyst used by the following formula.
Formula: Weight of ruthenium = Weight of catalyst used × Atomic weight of ruthenium ÷ Molecular weight of catalyst used Next, the weight of the obtained hydrolyzable silyl group-containing polymer is calculated by the following formula while considering the silyl group introduction rate. .
Formula: Weight of hydrolyzable silyl group-containing polymer = weight of allyl group-containing polymer + weight of silane compound reacted at the terminal Finally, the ruthenium content in the hydrolyzable silyl group-containing polymer is calculated by the following formula. do.
Formula: Ruthenium content ratio (ppm) = ruthenium weight ÷ (ruthenium weight + weight of hydrolyzable silyl group-containing polymer) × 1,000,000

(Synthesis example 1)
Using a mixture of a polyoxypropylene diol having a number average molecular weight of about 4,500 and a polyoxypropylene triol having a number average molecular weight of about 4,500 in a weight ratio of 60:40 as an initiator, zinc hexacyanocobaltate glyme complex was used to obtain propylene oxide. to obtain polyoxypropylene having a number average molecular weight of 19,000 and having hydroxyl groups at the ends.
A methanol solution of 1.2 equivalents of sodium methoxide is added to the hydroxyl groups of this polyoxypropylene to distill off the methanol, and 1.5 equivalents of 3-chloro-1-propene are added to remove terminal hydroxyl groups. was converted to an allyl group. After adding n-hexane and water to the obtained unpurified allyl group-terminated polyoxypropylene and mixing and stirring, the water was removed by centrifugation, and the hexane was devolatilized under reduced pressure from the resulting hexane solution to remove the hexane in the polymer. of metal salts were removed. Polyoxypropylene (A-1) having an allyl group at the terminal was thus obtained.

(Synthesis example 2)
Polyoxypropylene glycol with a number average molecular weight of about 2,000 is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to produce polyoxypropylene with a number average molecular weight of 27,900 having hydroxyl groups at the ends. Obtained. A methanol solution of sodium methoxide in an amount of 1.1 molar equivalents relative to the hydroxyl groups of this polyoxypropylene was added and distilled off. Converted. Unreacted propargyl bromide was removed by vacuum devolatilization. The obtained unpurified propargyl group-terminated polyoxypropylene was mixed with n-hexane and water and stirred, and then the water was removed by centrifugation. Metal salts were removed. As a result, polyoxypropylene (A-2) having propargyl groups at the ends was obtained.

(Example 1)
100 parts by weight of polymer (A-1) and 2.5 parts by weight of hexane were added to a glass reactor equipped with a stirrer, a reflux condenser and a thermometer, and azeotropic dehydration was carried out at 90°C. Hexane was distilled off under reduced pressure and the residue was replaced with nitrogen. The temperature was lowered to 45° C., 26.1 parts by weight of trimethoxyvinylsilane (10.0 mol times the terminal allyl group) was added, and then Grubbs Catalyst (registered trademark) 1st Generation (manufactured by Sigma-Aldrich) was added as a reaction catalyst. 0.4 parts by weight (0.1 mol times the terminal allyl group) was added to initiate the reaction. Two hours after the start of the reaction, the completion of the reaction was confirmed by ¹ H-NMR measurement, and the volatile components were distilled off to obtain polyoxypropylene (B-1) having trimethoxysilyl groups at the ends. The silyl group introduction rate in the polymer was 46%, and the molar ratio of the α-body structure and the β-body structure was 0:100.

(Example 2)
100 parts by weight of polymer (A-1) and 2.5 parts by weight of hexane were added to a glass reactor equipped with a stirrer, a reflux condenser and a thermometer, and azeotropic dehydration was carried out at 90°C. Hexane was distilled off under reduced pressure and the residue was replaced with nitrogen. The temperature was lowered to 45° C., 26.1 parts by weight of trimethoxyvinylsilane (10.0 mol times the terminal allyl group) was added, and then Grubbs Catalyst (registered trademark) 1st Generation (manufactured by Sigma-Aldrich) was added as a reaction catalyst. 4 parts by weight (0.1 mol times the amount of the terminal allyl group) was added, and the reaction was carried out while bubbling nitrogen through the reaction solution. After 4 hours from the start of the reaction, completion of the reaction was confirmed by ¹ H-NMR measurement, and volatile components were distilled off to obtain polyoxypropylene (B-2) having a trimethoxysilyl group at the end. The silyl group introduction rate in the polymer was 83%, and the molar ratio of the α-body structure and the β-body structure was 0:100.

(Example 3)
100 parts by weight of polymer (A-1) and 2.5 parts by weight of hexane were added to a glass reactor equipped with a stirrer, a reflux condenser and a thermometer, and azeotropic dehydration was carried out at 90°C. Hexane was distilled off under reduced pressure and the residue was replaced with nitrogen. The temperature was lowered to 45° C., and 26.1 parts by weight of trimethoxyvinylsilane (10.0 mol times the terminal allyl group) was added, followed by 1 part of Grubbs Catalyst (registered trademark) 2nd Generation (manufactured by Sigma-Aldrich) as a reaction catalyst. .5 parts by weight (0.1 mol times the amount of the terminal allyl group) was added, and the reaction was carried out while bubbling nitrogen through the reaction solution. After 4 hours from the start of the reaction, completion of the reaction was confirmed by ¹ H-NMR measurement, and volatile components were distilled off to obtain polyoxypropylene (B-3) having a trimethoxysilyl group at the end. The silyl group introduction rate in the polymer was 38%, and the molar ratio of the α-body structure and the β-body structure was 0:100.

(Example 4)
100 parts by weight of polymer (A-1) and 2.5 parts by weight of hexane were added to a glass reactor equipped with a stirrer, a reflux condenser and a thermometer, and azeotropic dehydration was carried out at 90°C. Hexane was distilled off under reduced pressure and the residue was replaced with nitrogen. The temperature was lowered to 45° C., and 26.1 parts by weight of trimethoxyvinylsilane (10.0 mol times the terminal allyl group) was added, followed by Hoveyda-Grubbs Catalyst (registered trademark) 2nd Generation (manufactured by Sigma-Aldrich) as a reaction catalyst. was added in an amount of 1.1 parts by weight (0.1 times by mole with respect to the terminal allyl group), and the reaction was carried out while bubbling nitrogen through the reaction solution. After 5 hours from the start of the reaction, completion of the reaction was confirmed by ¹ H-NMR measurement, and volatile components were distilled off to obtain polyoxypropylene (B-4) having trimethoxysilyl groups at the ends. The silyl group introduction rate in the polymer was 63%, and the molar ratio of the α-body structure and the β-body structure was 0:100.

(Comparative example 1)
100 parts by weight of polymer (A-2) and 2.5 parts by weight of hexane were added to a glass reactor equipped with a stirrer, a reflux condenser and a thermometer, and azeotropic dehydration was carried out at 90°C. Hexane was distilled off under reduced pressure and the residue was replaced with nitrogen. Raise the temperature to 110° C., add 0.01 parts by weight of a platinum divinyldisiloxane complex (3% by weight isopropanol solution in terms of platinum) (0.1×10 ³ mole times the terminal propargyl group in terms of platinum), and 1.73 parts by weight of trimethoxysilane (1.4 mol times the terminal propargyl group) was added to carry out a hydrosilylation reaction. After 2.5 hours from the start of the reaction, the completion of the reaction was confirmed by ¹ H-NMR measurement, unreacted trimethoxysilane was distilled off under reduced pressure, and polyoxypropylene (C- 1) was obtained. The silyl group introduction rate in the polymer was 99%, and the molar ratio of the α-body structure and the β-body structure was 49:51.

From Examples 1 to 4 shown in Table 1, a polymer having a hydrolyzable silyl group can be produced by subjecting a polymer having a vinyl group to a metathesis reaction of trimethoxyvinylsilane in the presence of a catalyst. I understand. It is also found that 80 mol % or more of the hydrolyzable silyl groups in the polymers obtained in each example have a β structure. On the other hand, in Comparative Example 1, in which a hydrosilylation reaction was used to introduce a hydrolyzable silyl group into a polymer having a propargyl group, it was found that the α-form structure and the β-form structure were produced at a ratio of about 1:1.
From Example 2 among Examples 1 to 4, it can be seen that a very high silyl group introduction rate of 83% can be achieved by using the first generation Grubbs catalyst and performing the above reaction while bubbling nitrogen.

Claims

Metathesis reaction of a polymer having a vinyl group with a silane compound having a vinyl group and a hydroxyl group or a hydrolyzable group on a silicon atom in the presence of a catalyst. Production method.
The production method according to claim 1, wherein the temperature during the metathesis reaction is 60°C or less.
The production method according to claim 1 or 2, wherein the metathesis reaction is performed while inert gas is bubbled through the reaction system.
The production method according to any one of claims 1 to 3, wherein the catalyst is a Grubbs catalyst.
The silane compound is represented by the formula: CH 2 ═CH—Si(R 1 ) 3-a (X) a (wherein R 1 is a substituted or unsubstituted hydrocarbon having 1 to 20 carbon atoms). X represents a hydroxyl group or a hydrolyzable group, and a represents 1, 2, or 3.), the production method according to any one of claims 1 to 4.
A polyoxyalkylene polymer having a hydrolyzable silyl group,
80 mol % or more of the hydrolyzable silyl groups have a structure represented by the formula: —CH═CH—Si(R 1 ) 3-a (X) a (wherein R 1 is a carbon atom represents a substituted or unsubstituted hydrocarbon group of numbers 1 to 20, X represents a hydroxyl group or a hydrolyzable group, and a represents 1, 2, or 3), a polyoxyalkylene polymer.
7. The polyoxyalkylene polymer according to claim 6, wherein the structure is represented by -O-CH 2 -CH=CH-Si(R 1 ) 3-a (X) a .
The polyoxyalkylene polymer according to claim 6 or 7, which contains ruthenium.
The polyoxyalkylene polymer according to claim 8, which has a ruthenium content of 10 to 2,000 ppm.
A curable composition containing the polyoxyalkylene polymer according to any one of claims 6 to 9.
The curable composition according to claim 10, further containing a curing catalyst.
A cured product of the curable composition according to claim 11 .