JP7649664B2 - Method for producing organic polymer, organic polymer, curable composition, and cured product - Google Patents

Description

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

Organic polymers having a silicon-containing group (hereinafter referred to as "hydrolyzable silyl group") that has a hydroxyl group or a hydrolyzable group on a silicon atom and can form a siloxane bond are known as moisture-reactive polymers, and are included in many industrial products such as adhesives, sealants, coating materials, paints, and pressure sensitive adhesives, and are used in a wide range of fields. As such organic polymers containing hydrolyzable silyl groups, various polymers whose main chain skeletons are polyoxyalkylene polymers, saturated hydrocarbon polymers, (meth)acrylic acid ester copolymers, etc. are known.

As a method for producing an organic polymer containing hydrolyzable silyl groups, for example, a method is known in which an epoxy compound is subjected to ring-opening polymerization to synthesize a polyoxyalkylene polymer having a hydroxyl group at the end, the hydroxyl group is then converted into a carbon-carbon double bond, and the carbon-carbon double bond is subjected to a hydrosilylation reaction with a silane compound to introduce a hydrolyzable silyl group into the polymer (see, for example, Patent Document 1). However, the hydrolyzable silyl group-containing polymer obtained by this method does not necessarily have sufficient curability, and there is a demand for improving this.

Patent Document 2 describes a method of introducing hydrolyzable silyl groups into a polymer by converting the hydroxyl groups of a polyoxyalkylene polymer into carbon-carbon triple bonds and then subjecting the carbon-carbon triple bonds to a hydrosilylation reaction with a silane compound, and describes that the resulting polymer has hydrolyzable silyl groups directly bonded to the carbon atoms that form the carbon-carbon double bonds and exhibits fast curing properties.

Japanese Unexamined Patent Publication No. 52-73998 International Publication No. 2019/189491

According to the manufacturing method described in Patent Document 2, it is possible to produce a polymer that has a hydrolyzable silyl group directly bonded to a carbon atom that forms a carbon-carbon double bond and exhibits fast curing properties, but the curing properties are still insufficient, and improvements are required.

In view of the above-mentioned current situation, the present invention aims to provide a new method for producing an organic polymer having a hydrolyzable silyl group directly bonded to a carbon atom forming a carbon-carbon double bond, the organic polymer having improved curability, as well as a polymer obtainable by the production method, a curable composition containing the polymer, and a cured product thereof.

The present inventors discovered that it is possible to produce a polymer having a hydrolyzable silyl group and a carbon-carbon double bond adjacent to a silicon atom in the silyl group by using a urethanization reaction using an isocyanate compound, rather than a hydrosilylation reaction of a carbon-carbon triple bond as described in Patent Document 2, and thus arrived at the present invention.

（各式中、Ｒ^１、Ｒ^２、及びＲ^３のうちいずれか１つの基が、式：－ＳｉＲ_ａＹ_３－ａで表される加水分解性シリル基を表し、残り２つの基が、同一又は異なって、水素原子、又は炭素数１～２０の置換若しくは無置換の炭化水素基を表す。ｎは、１～５の整数を表す。Ｒは、炭素数１～２０の置換又は無置換の炭化水素基を表す。Ｙは、水酸基又は加水分解性基を表す。ａは、０、１又は２である。）
好ましくは、前記反応の前に、式（１）で表される化合物を精製して、前記式（１）で表される化合物全体のうちＲ^１が前記加水分解性シリル基を表す化合物の占める割合を高める工程を更に含む。
また本発明は、下記式（２）：

（式中、Ｒ^１、Ｒ^２、及びＲ^３のうちいずれか１つの基が、式：－ＳｉＲ_ａＹ_３－ａで表される加水分解性シリル基を表し、残り２つの基が、同一又は異なって、水素原子、又は炭素数１～２０の置換若しくは無置換の炭化水素基を表す。ｎは、１～５の整数を表す。Ｒは、炭素数１～２０の置換又は無置換の炭化水素基を表す。Ｙは、水酸基又は加水分解性基を表す。ａは、０、１又は２である。）
で表される構造を有する有機重合体であって、Ｒ^１、Ｒ^２、及びＲ^３によって表される加水分解性シリル基全体のうち、Ｒ^１によって表される加水分解性シリル基の占める割合が、５５モル％以上１００モル％以下である、有機重合体にも関する。
好ましくは、前記有機重合体の重合体骨格が、ポリオキシアルキレン系重合体である。
さらに本発明は、前記有機重合体を含有する硬化性組成物、又は、該硬化性組成物を硬化させた硬化物にも関する。好ましくは、前記硬化性組成物は、シラノール縮合触媒を更に含有する。 That is, the present invention relates to a method for producing an organic polymer having a structure represented by the following formula (2), which comprises a step of reacting a hydroxyl group-containing organic polymer with a compound represented by the following formula (1).

(In each formula, any one of R ¹ , R ² , and R ³ represents a hydrolyzable silyl group represented by the formula: -SiR _a Y _3-a , and the remaining two groups, which may be the same or different, represent a hydrogen atom, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. n represents an integer of 1 to 5. R represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Y represents a hydroxyl group or a hydrolyzable group. a is 0, 1, or 2.)
Preferably, the method further comprises a step of purifying the compound represented by formula (1) prior to the reaction to increase the proportion of the compound in which R ¹ represents the hydrolyzable silyl group in all the compounds represented by formula (1).
The present invention also relates to a compound represented by the following formula (2):

(In the formula, any one of R ¹ , R ² , and R ³ represents a hydrolyzable silyl group represented by the formula: -SiR _a Y _3-a , and the remaining two groups, which may be the same or different, represent a hydrogen atom, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. n represents an integer of 1 to 5. R represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Y represents a hydroxyl group or a hydrolyzable group. a is 0, 1, or 2.)
The present invention also relates to an organic polymer having a structure represented by the following formula: wherein the proportion of hydrolyzable silyl groups represented by R ¹ among all hydrolyzable silyl groups represented by R ¹ , R ² , and R ³ is 55 mol % or more and 100 mol % or less.
Preferably, the polymer backbone of the organic polymer is a polyoxyalkylene polymer.
The present invention further relates to a curable composition containing the organic polymer, or a cured product obtained by curing the curable composition. Preferably, the curable composition further contains a silanol condensation catalyst.

According to the present invention, it is possible to provide a novel method for producing an organic polymer having a hydrolyzable silyl group directly bonded to a carbon atom that forms a carbon-carbon double bond, the organic polymer having improved curability, as well as a polymer obtainable by the production method, a curable composition containing the polymer, and a cured product thereof.
According to a preferred embodiment of the present invention, an organic polymer having hydrolyzable silyl groups directly bonded to carbon atoms forming a carbon-carbon double bond can be produced in which the proportion of hydrolyzable silyl groups represented by ^R1 among all the hydrolyzable silyl groups is high.

Hereinafter, an embodiment of the present invention will be described in detail.
According to the production method of this embodiment, an organic polymer having a hydroxyl group is reacted with a compound having an isocyanate group, a carbon-carbon double bond, and a hydrolyzable silyl group directly bonded to the carbon atom forming the double bond (a compound represented by formula (1)) to form a urethane bond, thereby producing an organic polymer having a hydrolyzable silyl group directly bonded to the carbon atom forming the carbon-carbon double bond (an organic polymer having a structure represented by formula (2)).

(Hydroxyl Group-Containing Organic Polymer)
The organic polymer, which is a starting material, is a polymer having a hydroxyl group. The organic polymer has a polymer skeleton composed of a plurality of repeating units. The polymer skeleton of the organic polymer may be linear or branched. The position at which the hydroxyl group is bonded to the polymer skeleton is not particularly limited, but it is preferably the terminal of the polymer skeleton.

There are no particular limitations on the polymer backbone of the organic polymer, and various polymer backbones can be used. Specific examples of polymer backbones include polyoxyalkylene polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymers, and polyoxypropylene-polyoxybutylene copolymers; ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, etc., polychloroprene, polyisoprene, copolymers of isoprene or butadiene and acrylonitrile and/or styrene, etc., copolymers of polybutadiene, isoprene or butadiene and acrylonitrile and styrene, etc., and polyolefin polymers thereof. Examples of the organic polymers include saturated hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating a copolymer; polyester polymers; vinyl polymers such as (meth)acrylic acid ester polymers obtained by radical polymerization of (meth)acrylic acid ester monomers such as ethyl (meth)acrylate and butyl (meth)acrylate, and polymers obtained by radical polymerization of monomers such as (meth)acrylic acid monomers, vinyl acetate, acrylonitrile, and styrene; graft polymers obtained by polymerizing vinyl monomers in the above-mentioned polymers; polysulfide polymers; polyamide polymers; polycarbonate polymers; and diallyl phthalate polymers. The above-mentioned polymers may be mixed in block form, graft form, etc. Among these, saturated hydrocarbon polymers, polyoxyalkylene polymers, and (meth)acrylic acid ester polymers are preferred because they have a relatively low glass transition temperature and the resulting cured product has excellent cold resistance, polyoxyalkylene polymers are more preferred, and polyoxypropylene is particularly preferred.

The organic polymer may be a polymer having one type of polymer backbone, or a mixture of two or more types of polymers having different polymer backbones. The mixture may be a mixture of polymers produced separately, or may be a mixture produced simultaneously to obtain any mixture composition.

The number average molecular weight of the organic polymer is not particularly limited, but is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and even more preferably 3,000 to 30,000 in terms of polystyrene equivalent molecular weight in GPC. If the number average molecular weight is 3,000 or more, the relative amount of hydrolyzable silyl groups to the entire polymer is in an appropriate range, which is desirable in terms of production costs. Furthermore, if the number average molecular weight is 100,000 or less, it is easy to achieve a desirable viscosity in terms of workability. The number average molecular weight can be determined in terms of polystyrene equivalent by GPC measurement.

The molecular weight distribution (Mw/Mn) of the organic polymer is not particularly limited, but is preferably narrow. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, and particularly preferably 1.4 or less. 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 weight average molecular weight calculated in terms of polystyrene by GPC measurement.

Next, a method for producing an organic polymer having a hydroxyl group will be described.
(Polyoxyalkylene polymer)
When the polymer backbone of the hydroxyl-containing organic polymer is a polyoxyalkylene-based polymer, the polymer can be produced by polymerizing an epoxy compound with an initiator having a hydroxyl group by a conventionally known method. This produces a hydroxyl-terminated polyoxyalkylene-based polymer. Although the specific polymerization method is not particularly limited, a polymerization method using a composite metal cyanide complex catalyst such as zinc hexacyanocobaltate glyme complex is preferred because it produces a polymer with a small molecular weight distribution (Mw/Mn).

Examples of initiators having a hydroxyl group include, but are not limited to, organic compounds having one or more hydroxyl groups, such as ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, low molecular weight polyoxypropylene triol, allyl alcohol, low molecular weight polyoxypropylene monoallyl ether, low molecular weight polyoxypropylene monoalkyl ether, methanol, ethanol, propanol, butanol, pentanol, and hexanol.

The epoxy compound is not particularly limited, but 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.

((Meth)acrylic acid ester polymer)
When the polymer skeleton of the hydroxyl group-containing organic polymer is a (meth)acrylic acid ester polymer, examples of the method for producing the hydroxyl group-containing organic polymer include (I) a method of copolymerizing a compound having a polymerizable unsaturated group and a hydroxyl group (e.g., 2-hydroxyethyl acrylate) together with a monomer having a (meth)acrylic structure to obtain a polymer, and (II) a method of polymerizing a monomer having a (meth)acrylic structure by a living radical polymerization method such as atom transfer radical polymerization to obtain a polymer, and then introducing a hydroxyl group into any position (preferably a molecular chain terminal) of the obtained polymer.

(Saturated Hydrocarbon Polymer)
When the polymer backbone of the hydroxyl group-containing organic polymer is a saturated hydrocarbon polymer, examples of the method for producing the hydroxyl group-containing organic polymer include a method in which an olefin compound having 2 to 6 carbon atoms, such as ethylene, propylene, 1-butene, or isobutylene, is polymerized as a main monomer to obtain a polymer, and then a hydroxyl group is introduced into any position (preferably the molecular chain terminal) of the obtained polymer.

(Silane compound represented by formula (1))
The compound to be reacted with the hydroxyl group-containing organic polymer is a compound represented by the following formula (1), which is a compound having an isocyanate group, a carbon-carbon double bond, and a hydrolyzable silyl group directly bonded to the carbon atom that forms the double bond (hereinafter, also referred to as a silane compound).

In the formula, any one of R ¹ , R ² , and R ³ represents a hydrolyzable silyl group represented by the formula: -SiR _a Y _3-a , and the remaining two groups, which may be the same or different, represent a hydrogen atom, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 1 to 5.

The silane compound may be any one of a compound in which ^R1 represents a hydrolyzable silyl group, a compound in which ^R2 represents a hydrolyzable silyl group, and a compound in which ^R3 represents a hydrolyzable silyl group, or may be a mixture of a compound in which ^R1 represents a hydrolyzable silyl group, a compound in which ^R2 represents a hydrolyzable silyl group, and a compound in which ^R3 represents a hydrolyzable silyl group.

From the viewpoint of the curability of the produced hydrolyzable silyl group-containing organic polymer, the ratio of the compound in which R ¹ represents the hydrolyzable silyl group to the entire silane compounds is preferably 55 mol% to 100 mol%, more preferably 70 mol% to 100 mol%, even more preferably 80 mol% to 100 mol%, and particularly preferably 90 mol% to 100 mol%. In particular, it is most preferable that the silane compounds are only compounds in which R ¹ represents the hydrolyzable silyl group.

In the formula -SiR _a Y _3-a representing the hydrolyzable silyl group, R 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, even more preferably 1 to 6, still more preferably 1 to 3, and particularly preferably 1 or 2. When the hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include halogen groups such as a chloro group, alkoxy groups such as a methoxy group, and amino groups such as an N,N-diethylamino group.

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

Y represents a hydroxyl group or a hydrolyzable group. Examples of Y include hydroxyl group, hydrogen, halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, alkenyloxy group, etc. The alkoxy group, etc. may have a substituent. Since they are mildly hydrolyzable and easy to handle, alkoxy groups are preferred, methoxy groups, ethoxy groups, n-propoxy groups, and isopropoxy groups are more preferred, methoxy groups and ethoxy groups are even more preferred, and methoxy groups are particularly preferred. Only one type of group may be used as Y, or two or more types of groups may be used in combination.

In the above formula, a represents 0, 1, or 2. Preferably, it is 0 or 1.

In the formula (1), two groups among R ¹ , R ² , and R ³ are not hydrolyzable silyl groups and represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. The two groups may be the same or different. As the hydrocarbon group, for example, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms is preferable. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 4. The number of carbon atoms of the aryl group is preferably 6 to 12, more preferably 6 to 10. The number of carbon atoms of the aralkyl group is preferably 7 to 12.

In the formula (1), the two groups that are not hydrolyzable silyl groups are specifically hydrogen atoms; alkyl groups such as methyl, ethyl, and cyclohexyl; aryl groups such as phenyl and tolyl; and aralkyl groups such as benzyl and phenethyl. Of these, hydrogen atoms and methyl groups are preferred, and hydrogen atoms are more preferred.

In the formula (1), n represents an integer of 1 to 5. An integer of 1 to 3 is preferred, 1 or 2 is more preferred, and 1 is most preferred.

Specific examples of the silane compound include, for example, 3-isocyanato-1-(trimethoxysilyl)-1-propene, 3-isocyanato-2-(trimethoxysilyl)-1-propene, 3-isocyanato-1-(triethoxysilyl)-1-propene, 3-isocyanato-2-(triethoxysilyl)-1-propene, 3-isocyanato-1-(tris(2-propenyloxy))-1-propene, 3-isocyanato-2-(tris(2-propenyloxy))-1-propene, 3-isocyanato-1-(triacetoxysilyl)-1-propene, 3-isocyanato-2 -(triacetoxysilyl)-1-propene, 3-isocyanato-1-(methyldimethoxysilyl)-1-propene, 3-isocyanato-2-(methyldimethoxysilyl)-1-propene, 3-isocyanato-1-(methyldiethoxysilyl)-1-propene, 3-isocyanato-2-(methyldiethoxysilyl)-1-propene, 3-isocyanato-1-(dimethoxyethylsilyl)-1-propene, 3-isocyanato-2-(dimethoxyethylsilyl)-1-propene, 3-isocyanato-1-(diethoxyethylsilyl)-1-propene, 3-isocyanato-2 -(diethoxyethylsilyl)-1-propene, 3-isocyanato-1-((chloromethyl)dimethoxysilyl)-1-propene, 3-isocyanato-2-((chloromethyl)dimethoxysilyl)-1-propene, 3-isocyanato-1-((chloromethyl)diethoxysilyl)-1-propene, 3-isocyanato-2-((chloromethyl)diethoxysilyl)-1-propene, 3-isocyanato-1-((methoxymethyl)dimethoxysilyl)-1-propene, 3-isocyanato-2-((methoxymethyl)dimethoxysilyl)-1-propene, 3-isocyanato -1-((methoxymethyl)diethoxysilyl)-1-propene, 3-isocyanato-2-((methoxymethyl)diethoxysilyl)-1-propene, 3-isocyanato-1-((N,N-diethylaminomethyl)dimethoxysilyl)-1-propene, 3-isocyanato-2-((N,N-diethylaminomethyl)dimethoxysilyl)-1-propene, 3-isocyanato-1-((N,N-diethylaminomethyl)diethoxysilyl)-1-propene, 3-isocyanato-2-((N,N-diethylaminomethyl)diethoxysilyl)-1-propene, and the like. Silane compounds may be used alone or in combination of two or more kinds.

The amount of the silane compound used can be appropriately determined taking into consideration the amount of hydroxyl groups in the hydroxyl-containing organic polymer and the amount of hydrolyzable silyl groups to be introduced, and is not particularly limited. For example, the amount is preferably 0.1 to 10 times by mole, more preferably 0.3 to 5 times by mole, and even more preferably 0.5 to 3 times by mole, relative to the amount of hydroxyl groups in the hydroxyl-containing organic polymer.

The silane compound can be synthesized, for example, as follows. First, a hydrolyzable silyl group-containing silane compound, such as trimethoxysilane, is added to a carbon-carbon triple bond-containing halogenated hydrocarbon, such as propargyl chloride, by a hydrosilylation reaction. The resulting product is reacted with an alkali metal cyanate salt in the presence of an alcohol compound to convert the halogen group to a carbamate group. The resulting carbamate group is converted to an isocyanate group (isocyanation), thereby obtaining the silane compound represented by formula (1).

It is preferable to purify the silane compound represented by formula (1) before subjecting it to the urethanization reaction described below, thereby increasing the proportion of the compound in which R ¹ represents the hydrolyzable silyl group in the silane compound. Such a purification step can be carried out by utilizing a conventionally known method, for example, distillation or recrystallization.

(Urethanization reaction)
The hydroxyl group-containing organic polymer is reacted with an isocyanate group of the compound represented by formula (1) to form a urethane bond by a urethanization reaction, whereby the desired organic polymer having a hydrolyzable silyl group can be produced.

The urethanization reaction may be carried out without using a urethanization catalyst, but may be carried out in the presence of a urethanization catalyst in order to improve the reaction rate or the reaction rate. As such a urethanization catalyst, for example, a conventionally known urethanization catalyst such as the catalysts listed in Polyurethanes: Chemistry and Technology, Part I, Table 30, Chapter 4, Saunders and Frisch, Interscience Publishers, New York, 1963, can be used. Specific examples include, but are not limited to, base catalysts such as organic tin compounds, bismuth compounds, and organic amines.

As a urethane-forming catalyst, organotin compounds are preferred due to their high activity. Specific examples include tin octylate, tin stearate, dibutyltin dioctoate, dibutyltin dioleyl maleate, dibutyltin dibutyl maleate, dibutyltin dilaurate, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl distannoxane, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin bis(o-phenylphenoxide), dibutyltin oxide, dibutyltin bis(triethoxysilicate), dibutyltin distearate, dibutyltin bis(isononyl-3-mercaptopropionate), dibutyltin bis(isooctylmercaptopropionate), dibutyltin bis(isooctylthioglycolate), dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate, and dioctyltin diversatate. Furthermore, urethanization catalysts that are less active against hydrolyzable silyl groups are preferred, and from this viewpoint, organotin compounds containing sulfur atoms are preferred, and among these, dibutyltin bis(isononyl-3-mercaptopropionate), dibutyltin bis(isooctylmercaptopropionate), and dibutyltin bis(isooctylthioglycolate) are particularly preferred.

The amount of urethane catalyst to be added can be appropriately determined by those skilled in the art, but from the viewpoint of reaction activity, it is preferably 1 to 1000 ppm, more preferably 10 to 100 ppm, per 100 parts by weight of the hydroxyl group-containing organic polymer. In this range, sufficient reaction activity can be obtained, and the physical properties of the hydrolyzable silyl group-containing organic polymer produced can be well maintained.

The urethanization reaction can be carried out without using a solvent, but an organic solvent may be added to dissolve the hydroxyl-containing organic polymer, the silane compound, and the urethanization catalyst uniformly, and to easily control the temperature of the reaction system and add the urethanization catalyst.

When an organic solvent is used, the type is not particularly limited and may be selected appropriately. Examples of the organic solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, cyclooctane, cyclodecane, cyclododecane, and petroleum ether; 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; and ether solvents such as tetrahydrofuran (THF) and tetrahydropyran (THP). Only one type of organic solvent may be used, or two or more types may be used in combination.

The temperature of the urethane reaction can be set appropriately by those skilled in the art, but is preferably 50°C or higher and 120°C or lower, and more preferably 70°C or higher and 100°C or lower. The reaction time can also be set appropriately, but it is preferable to adjust the reaction time along with the temperature conditions so that unintended condensation reactions between polymers do not proceed. Specifically, the reaction time is preferably 15 minutes or higher and 5 hours or lower, and more preferably 30 minutes or higher and 3 hours or lower.

式（２）中、Ｒ^１、Ｒ^２、Ｒ^３、及びｎは、前記式（１）について上述したものと同じである。 (Hydrolyzable Silyl Group-Containing Organic Polymer)
By the production method described above in detail, a polymer having a structure represented by formula (2) can be produced as an organic polymer having a hydrolyzable silyl group.

In formula (2), R ¹ , R ² , R ³ and n are the same as defined above for formula (1).

The organic polymer having the structure represented by the formula (2) has a hydrolyzable silyl group and a carbon-carbon double bond adjacent to the silicon atom in the silyl group, which are bonded to the polymer skeleton via a urethane bond. The hydrolyzable silyl group-containing organic polymer that can be produced by this embodiment can exhibit faster curing properties than the hydrolyzable silyl group-containing organic polymer disclosed in Patent Document 2.

The hydrolyzable silyl group of the organic polymer according to this embodiment corresponds to the hydrolyzable silyl group in the silane compound, and can be represented by -SiR _a Y _3-a . In the formula, R, Y, and a are as described above. Specific examples of the hydrolyzable silyl group of the organic polymer include, for example, a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a methyldimethoxysilyl group, a methyldiethoxysilyl group, a dimethoxyethylsilyl group, a (chloromethyl)dimethoxysilyl group, a (chloromethyl)diethoxysilyl group, a (methoxymethyl)dimethoxysilyl group, a (methoxymethyl)diethoxysilyl group, a (N,N-diethylaminomethyl)dimethoxysilyl group, and a (N,N-diethylaminomethyl)diethoxysilyl group. Only one type of hydrolyzable silyl group may be present, or two or more types may be present in combination.

From the viewpoint of the curability of the hydrolyzable silyl group-containing organic polymer, it is preferable that the ratio of the hydrolyzable silyl group represented by R ¹ to the total of the hydrolyzable silyl groups represented by R ¹ , R ² , and R ³ in the formula (2) is 55 mol % or more and 100 mol % or less. An organic polymer having such a high ratio of the hydrolyzable silyl group represented by R ¹ in the formula (2) has not been reported so far. Such an organic polymer also constitutes one aspect of this embodiment. In addition, when R ¹ represents a hydrolyzable silyl group, the polymer backbone and the hydrolyzable silyl group are bonded to the same carbon atom among the two carbon atoms constituting the carbon-carbon double bond.

Further, the ratio of the hydrolyzable silyl group represented by the R ¹ is more preferably 70 mol % or more and 100 mol % or less, further preferably 80 mol % or more and 100 mol % or less, and particularly preferably 90 mol % or more and 100 mol % or less. The high ratio of the hydrolyzable silyl group represented by R ¹ as described above can be achieved by controlling the position of the hydrolyzable silyl group in the silane compound as the raw material, that is, by increasing the ratio of the compound in which R ¹ represents the hydrolyzable silyl group in the entire silane compound.

The details of the polymer skeleton of the hydrolyzable silyl group-containing organic polymer, the number average molecular weight, and the range of the molecular weight distribution are the same as those of the hydroxyl group-containing organic polymer, so they will not be described here.

(Curable Composition)
The above-mentioned hydrolyzable silyl group-containing organic polymer can constitute a curable composition containing the same.

(Silanol Condensation Catalyst)
The curable composition according to this embodiment preferably contains a silanol condensation catalyst for the purpose of promoting the reaction of hydrolyzing and condensing the hydrolyzable silyl group, i.e., the curing reaction.

As the silanol condensation catalyst, a conventionally known catalyst can be used, specifically, an organotin compound, a metal carboxylate, an amine compound, a carboxylic acid, an alkoxy metal, an inorganic acid, etc. can be used.

Specific examples of organic tin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), a reaction product of dibutyltin oxide and a silicate compound, a reaction product of dibutyltin oxide and a phthalic acid ester, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate), a reaction product of dioctyltin oxide and a silicate compound, and the like. In view of the recent increase in environmental interest, dioctyltin compounds are preferred. However, since the hydrolyzable silyl group-containing organic 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 can contain a silanol condensation catalyst (especially an amine compound, etc.) which is generally considered to be less active than an organic tin compound. The curable composition according to this embodiment can exhibit good curability even if it contains an amine compound.

Specific examples of metal carboxylates include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and calcium carboxylate. The carboxylate group can be a combination of the following carboxylic acids with various metals.

Specific examples of amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; 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.

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) and diisopropoxy titanium bis(ethylacetoacetate), aluminum compounds such as aluminum tris(acetylacetonate) and diisopropoxyaluminum ethylacetoacetate, and zirconium compounds such as zirconium tetrakis(acetylacetonate).

Other silanol condensation catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.

The silanol condensation catalyst may be used in combination of two or more different catalysts. For example, the use of the amine compound and a carboxylic acid in combination may have the effect of improving reactivity.

In addition, since the hydrolyzable silyl group of the polymer according to this embodiment has high activity, it is possible to reduce the amount of the silanol condensation catalyst, use a silanol condensation catalyst with low activity, or use aminosilane, an amino group-containing silane coupling agent, as the silanol condensation catalyst. Since aminosilane is usually added as an adhesion promoter, when aminosilane is used as a silanol condensation catalyst, a curable composition can be prepared without using a silanol condensation catalyst that is usually used. Therefore, it is preferable not to add other silanol condensation 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 silanol condensation catalyst.

The amount of the silanol condensation 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, per 100 parts by weight of the hydrolyzable silyl group-containing organic polymer. If the amount of the silanol condensation catalyst is less than 0.001 parts by weight, the reaction rate may be insufficient. On the other hand, if the amount of the silanol condensation catalyst is more than 20 parts by weight, the reaction rate is too fast, so the usable time of the composition is shortened, which tends to result in poor workability and poor storage stability. Furthermore, some silanol condensation catalysts may seep 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 silanol condensation catalyst used is 0.01 to 3.0 parts by weight, which ensures curability while maintaining a good surface condition of the cured product.

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. In addition, 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, antiozonants, phosphorus-based peroxide decomposers, lubricants, pigments, and fungicides.

(Filler)
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.

The amount of filler used is preferably 1 to 300 parts by weight, and more preferably 10 to 250 parts by weight, per 100 parts by weight of the hydrolyzable silyl group-containing organic polymer.

Organic or inorganic balloons may be added to reduce the weight (specific gravity) of the composition. 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 balloons used is preferably 0.1 to 100 parts by weight, more preferably 1 to 20 parts by weight, per 100 parts by weight of the hydrolyzable silyl group-containing organic polymer.

(Adhesion imparting agent)
An adhesion promoter may be added to the curable composition according to the present embodiment. As the adhesion promoter, a silane coupling agent or a reaction product of a silane coupling agent may be added.
Specific examples of the silane coupling agent include amino group-containing silanes such as γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane; γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-isopropyltrimethoxysilane. Examples of the adhesion promoter include isocyanate group-containing silanes such as cyanate propyl methyl dimethoxy silane, α-isocyanate methyl trimethoxy silane, α-isocyanate methyl dimethoxy methyl silane, mercapto group-containing silanes such as γ-mercapto propyl trimethoxy silane, γ-mercapto propyl triethoxy silane, γ-mercapto propyl methyl dimethoxy silane, and epoxy group-containing silanes such as γ-glycidoxy propyl trimethoxy silane, β-(3,4-epoxy cyclohexyl) ethyl trimethoxy silane. The adhesion promoter may be used alone or in combination of two or more kinds.

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, per 100 parts by weight of the hydrolyzable silyl group-containing organic polymer.

(Plasticizer)
A plasticizer may be added to the curable composition according to this embodiment. Specific examples of 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 and methyl acetylricinoleate; alkylsulfonic acid phenyl esters; phosphate ester compounds; trimellitic acid ester compounds; chlorinated paraffin; hydrocarbon oils such as alkyl diphenyls and partially hydrogenated terphenyls; process oils; and epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.

Polymer plasticizers can also be used. Specific examples of polymer 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 amount of plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and even more preferably 20 to 100 parts by weight, per 100 parts by weight of the hydrolyzable silyl group-containing organic polymer.

(Solvent, diluent)
A 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. When using a solvent or diluent, 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.

(Anti-sagging agent)
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 anti-sagging agent used is preferably 0.1 to 20 parts by weight per 100 parts by weight of the hydrolyzable silyl group-containing organic polymer.

(Antioxidants)
An antioxidant (antiaging agent) can be used in the curable composition according to this embodiment. Use of an antioxidant can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenol-based, monophenol-based, bisphenol-based, and polyphenol-based antioxidants. 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, based on 100 parts by weight of the hydrolyzable silyl group-containing organic polymer.

(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. 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 light stabilizer used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the hydrolyzable silyl group-containing organic polymer.

(Ultraviolet absorber)
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. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferred, and examples of the ultraviolet absorbers 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, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the hydrolyzable silyl group-containing organic polymer.

(Physical property adjuster)
The curable composition according to this embodiment may contain a physical property adjuster for adjusting the tensile properties of the cured product to be produced, 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 γ-glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as tris(trimethylsilyl)borate and tris(triethylsilyl)borate; silicone varnishes; and polysiloxanes. By using the physical property adjuster, the hardness of the curable composition according to this embodiment can be increased when cured, or conversely, the hardness can be reduced to provide a breaking elongation. The physical property adjuster may be used alone, or two or more types may be used in combination.

In particular, 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.

The amount of the property adjuster used is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the hydrolyzable silyl group-containing organic polymer.

(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 required. The tackifier resin is not particularly limited, and any commonly used resin can be used.

Specific examples include terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenol resins, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone-indene resins, rosin 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.

The amount of 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 hydrolyzable silyl group-containing organic polymer.

(Epoxy group-containing compound)
In the curable composition according to the present embodiment, a compound containing an epoxy group can be used. The use of a compound having an epoxy group can improve the restorability of the cured product. Examples of 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. Specific examples include epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, and epoxy butyl stearate. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight per 100 parts by weight of the hydrolyzable silyl group-containing organic polymer.

(Photocurable substances)
A photocurable material can be used in the curable composition according to this embodiment. 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 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 hydrolyzable silyl group-containing organic polymer.

(Oxygen-curable substances)
An oxygen-curable substance can be used in the curable composition according to the present embodiment. Examples of oxygen-curable substances include unsaturated compounds that can react with oxygen in the air, which react with oxygen in the air to form a cured film near the surface of the cured product, preventing the surface from becoming sticky and preventing dirt and dust from adhering to the surface of the cured product. Specific examples of 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 C5 to C8 diene polymers 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 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 hydrolyzable silyl group-containing organic polymer. As described in JP-A-3-160053, it is recommended that the oxygen-curing substance be used in combination with a photocuring substance.

(Epoxy resin)
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.

The ratio of the epoxy resin to the hydrolyzable silyl group-containing organic polymer is preferably in the range of 100/1 to 1/100 by weight (hydrolyzable silyl group-containing organic polymer/epoxy resin). If the ratio of hydrolyzable silyl group-containing organic polymer/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 if the ratio of hydrolyzable silyl group-containing organic polymer/epoxy resin 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 this embodiment. There are no particular limitations on the epoxy resin curing agent that can be used, and any commonly used epoxy resin curing agent can be used.

When using an epoxy resin hardener, the amount used is preferably in the range of 0.1 to 300 parts by weight per 100 parts by weight of 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 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 silanol condensation 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.

When the curable composition is a one-component type, all the ingredients are mixed in advance, so it is preferable to dehydrate and dry the ingredients containing water before use, or to dehydrate them by reducing pressure during mixing. In addition to the dehydration and drying method, the storage stability can be further improved by adding an alkoxysilane compound such as n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, or γ-glycidoxypropyltrimethoxysilane.

<Applications>
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 sound-proofing 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 therefore can be suitably used as a sealing material or an adhesive.

In addition, 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 back surface 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 sealants for joints in exterior materials such as sizing boards. It can be used for various applications such as adhesives, 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. For example, in automobiles, it can be used in a wide variety of applications such as adhesive installation of plastic covers, trims, flanges, bumpers, window mounting, interior parts, exterior parts, etc. Furthermore, it can be used as various types of sealing compositions and adhesive compositions because it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, resin moldings, etc., either alone or with the aid of a primer. 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 present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

The compounds shown in the synthesis examples were identified and the reaction rates and isomer ratios were calculated by ¹ H NMR measurement using the following nuclear magnetic resonance apparatus (NMR).
Equipment: AVANCE III HD500 type digital equipment (manufactured by BRUKER)

(Synthesis Example 1)
A 300 mL flask equipped with a stirrer, thermometer, and reflux condenser was charged with 150 g of toluene, 15.0 g (201.3 mmol) of propargyl chloride, and 0.072 g of platinum divinyldisiloxane complex (3 wt % isopropanol solution calculated as platinum), and heated to 60° C. under a nitrogen atmosphere. Next, 27.1 g (221.4 mmol) of trimethoxysilane was charged, heated to 80° C., and reacted for 1 hour. The mixture was analyzed by ¹ H-NMR spectrum measurement, and it was confirmed that the raw materials propargyl chloride and trimethoxysilane had disappeared. Distillation was performed to obtain 28.5 g (yield 72%) of the product 3-chloroprop-1-enyltrimethoxysilane (compound 1) as a mixture of two isomers.
These two isomers differ in the carbon atom to which the silyl group is bonded. As shown in the chemical formula below, of the two carbon atoms that form a carbon-carbon double bond, the isomer in which the silyl group is bonded to the carbon atom separated by two bonds from the chlorine atom is called the α form, and the isomer in which the silyl group is bonded to the carbon atom separated by three bonds from the chlorine atom is called the β form. It was confirmed that Compound 1 contains the α form and the β form in a molar ratio of 82:18.
It was confirmed that the β form did not contain cis isomers but only trans isomers.

(Synthesis Example 2)
In a 200 mL flask equipped with a stirrer, a thermometer, and a reflux condenser, 14.8 g (182.4 mmol) of potassium cyanate, 104 g of dimethylformamide, 30.6 g (155.4 mmol) of compound 1, and 10.4 g (323.3 mmol) of methanol were charged, and the mixture was heated to 90° C. under stirring under a nitrogen atmosphere, and then heated to 120° C. over 4 hours, and reacted at 120° C. for 3 hours. After removing the solids by filtration, the liquid mixture was distilled to obtain 17.2 g of compound 2 (47% yield) having a carbamate group and a trimethoxysilyl group as a mixture of two isomers. These isomers were analyzed by ¹ H-NMR spectroscopy, and it was confirmed that they had an α-form and a β-form in a molar ratio of 81:19.

(Synthesis Example 3)
In a 50 ml eggplant flask connected to a connecting tube and a Liebig condenser, 17.0 g (72.2 mmol) of compound 2 and 1.7 g of dibutyltin dilaurate were placed, and the mixture was heated to 220° C. while stirring with a magnetic stirrer and a stirrer, and then the system was decompressed using a vacuum pump, and the mixture was vaporized, and then cooled and liquefied by a Liebig condenser and collected in another eggplant flask. The mixture was analyzed by ¹ H-NMR spectrum measurement. As a result, it was confirmed that the mixture contained compound 2 and compound 3' in which the carbamate group was converted to an isocyanate group in a ratio of 69:31. Compound 3' had an α-form and a β-form in a molar ratio of 81:19. The mixture was further distilled to isolate compound 3, which contained only the α-form and did not contain the β-form. Compound 3 corresponds to the silane compound represented by the above formula (1), and among them, corresponds to the compound in which R ¹ represents a hydrolyzable silyl group.

(Synthesis Example 4)
Using a mixture of polyoxypropylene glycol having a number average molecular weight of about 4,500 and polyoxypropylene triol having a number average molecular weight of about 4,500 in a weight ratio of 60:40 as an initiator, propylene oxide was polymerized in the presence of a zinc hexacyanocobaltate glyme complex catalyst to obtain a hydroxyl-terminated polyoxypropylene having a number average molecular weight of 17,300 and a molecular weight distribution Mw/Mn of 1.28 having hydroxyl groups at the terminals (hereinafter referred to as Polymer A).

(Synthesis Example 5)
In a 100 mL flask equipped with a stirrer and a thermometer, 25 g of the polymer A obtained in Synthesis Example 4 and 2.5 mg of Neostan U-360 (manufactured by Nitto Kasei Co., Ltd.), which is a mercaptotin catalyst, were placed and heated under a nitrogen atmosphere. At 90° C., 0.61 molar equivalents of compound 3 were added relative to the hydroxyl groups of polymer A, and the mixture was stirred for 45 minutes to form a urethane bond by the reaction between the hydroxyl groups of polymer A and the isocyanate groups of compound 3, thereby obtaining polymer B having a structure represented by the following formula at its terminal. Polymer B corresponds to an organic polymer having a structure represented by formula (2) above, and among them, corresponds to an organic polymer in which R ¹ represents a hydrolyzable silyl group. In polymer B, the proportion of the hydrolyzable silyl group represented by R ¹ among all the hydrolyzable silyl groups is 100 mol %.
The reaction rate of the hydroxyl groups in Polymer B was calculated by ¹ H NMR analysis and found to be 66%.

(Synthesis Example 6)
Sodium methoxide was added in an amount of 0.95 molar equivalents relative to the hydroxyl groups of polymer A as a 28% methanol solution. After distilling off the methanol by vacuum devolatilization, 0.15 molar equivalents of allyl chloride was added relative to the hydroxyl groups of polymer A to convert the terminal hydroxyl groups to allyl groups, and 0.75 molar equivalents of propargyl bromide were added to convert the terminal hydroxyl groups to propargyl groups. Unpurified propargyl-terminated polyoxypropylene was dissolved in n-hexane, and aluminum silicate (Kyowa Kagaku Co., Ltd., Kyoward R700SEN-S) was mixed and stirred to adsorb the metal salt in the polymer to the aluminum silicate, after which the aluminum silicate was removed by filtration, and hexane was devolatilized under reduced pressure from the resulting hexane solution. As a result of the above, polyoxypropylene having a propargyl group at the end was obtained (hereinafter referred to as polymer C).

(Synthesis Example 7)
To 100 parts by weight of polymer C, 1.60 parts by weight of trimethoxysilane was added at 90° C., followed by 100 ppm of platinum divinyldisiloxane complex (3% by weight of platinum in isopropanol solution), and a hydrosilylation reaction was carried out. After the reaction was carried out at 90° C. until trimethoxysilane was completely consumed, volatile components were distilled off to obtain polyoxypropylene having a structure represented by the following formula at its terminal (hereinafter referred to as polymer D). Polymer D corresponds to the hydrolyzable silyl group-containing organic polymer disclosed in Patent Document 2.

(Example 1 and Comparative Example 1)
100 parts by weight of each polymer shown in Table 1 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.), 54 parts by weight of Whiten SB (heavy calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd.), 5 parts by weight of Typen R820 (titanium oxide, manufactured by Ishihara Sangyo Kaisha, Ltd.), 2 parts by weight of Disparlon 6500 (fatty acid amide wax, manufactured by Kusumoto Chemical Co., Ltd.), 1 part by weight of Tinuvin 770 (bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, manufactured by BASF), and 1 part by weight of Tinuvin 326 (2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, manufactured by BASF), to prepare A-171 (Moment After 2 parts by weight of A-1120 (manufactured by Momentive: vinyltrimethoxysilane), 3 parts by weight of A-1120 (manufactured by Momentive: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane), and 0.1 parts by weight of DBU (1,8-diazabicyclo[5,4,0]undecene-7) were added and mixed, the resulting composition was filled into a mold of about 5 mm thickness with a spatula, and the time when the surface was smoothed into a flat shape was recorded as the curing start time, and the time when the surface was touched with the spatula and the composition for evaluation no longer adhered to the spatula was recorded as the skinning time, and the curing time was measured. The results are shown in Table 1.

As is clear from Table 1, the curable composition of Example 1 containing Polymer B exhibited better curability than the curable composition of Comparative Example 1 containing Polymer D.

Claims (7)

A method for producing an organic polymer having a structure represented by the following formula (2), comprising a step of reacting a hydroxyl group-containing organic polymer with a compound represented by the following formula (1):

(In each formula, any one of R ¹ , R ² , and R ³ represents a hydrolyzable silyl group represented by the formula: -SiR _a Y _3-a , and the remaining two groups, which may be the same or different, represent a hydrogen atom, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. n represents an integer of 1 to 5. R represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Y represents a hydroxyl group or a hydrolyzable group. a is 0, 1, or 2.) The method according to claim 1, further comprising a step of purifying the compound represented by formula (1) prior to the reaction to increase the proportion of compounds in which R ¹ represents the hydrolyzable silyl group in all of the compounds represented by formula (1). The following formula (2):

(In the formula, any one of R ¹ , R ² , and R ³ represents a hydrolyzable silyl group represented by the formula: -SiR _a Y _3-a , and the remaining two groups, which may be the same or different, represent a hydrogen atom, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. n represents an integer of 1 to 5. R represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Y represents a hydroxyl group or a hydrolyzable group. a is 0, 1, or 2.)
An organic polymer having a structure represented by
An organic polymer, wherein the proportion of hydrolyzable silyl groups represented by R ¹ among all hydrolyzable silyl groups represented by R ¹ , R ² and R ³ is 55 mol % or more and 100 mol % or less. The organic polymer according to claim 3, wherein the polymer backbone of the organic polymer is a polyoxyalkylene polymer. A curable composition containing the organic polymer according to claim 3 or 4. The curable composition according to claim 5, further comprising a silanol condensation catalyst. A cured product obtained by curing the curable composition according to claim 5 or 6.